JP2007078889A - Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity to a blue violet laser, excellent in light stability and heat stability under a yellow safe light, having very high storage stability, and capable of efficiently forming a pattern with high definition, a pattern forming material and a photosensitive laminate obtained by laminating the photosensitive composition, and a pattern forming apparatus and a pattern forming method. <P>SOLUTION: The photosensitive composition contains at least a binder, a polymerizable compound, a heat crosslinking agent and a photopolymerization initiator compound, wherein the photopolymerization initiator compound contains an acridine derivative and an onium compound. The pattern forming material has a support and at least a photosensitive layer comprising the photosensitive composition on the support. The photosensitive laminate has a photosensitive layer comprising the photosensitive composition. The pattern forming apparatus is equipped with the photosensitive laminate and has at least a light illuminating means and a light modulating means. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive composition suitable for a dry film resist (DFR), a solder resist, a liquid solder resist and the like capable of forming an image by UV exposure. In particular, a pattern forming material and a photosensitive laminate using the photosensitive composition, a pattern forming apparatus provided with the photosensitive laminate, a high-definition wiring pattern, a permanent pattern (protective film, interlayer insulating film, solder resist) The present invention relates to a pattern forming method such as a pattern.

In the field of printed wiring boards, usually, a copper wiring pattern is first formed on a copper clad laminate using DFR. Further, it is soldered onto a wiring pattern on which components such as a semiconductor, a capacitor, and a resistor are formed. In this case, for example, in a soldering process such as IR reflow, in order to prevent the solder from adhering to an unnecessary part of soldering, a permanent pattern corresponding to the unnecessary part of soldering is used as a protective film and an insulating film. The method of forming is adopted. Further, a pattern forming material such as a solder resist is used as the permanent pattern of the protective film. For example, as a photopolymerization initiator, i) a photosensitive composition containing a bisacylphosphine oxide compound (see Patent Document 1), ii) a photosensitive composition containing an α-aminoacetophenone compound (see Patent Document 2), iii) a photo / thermosetting composition containing oxime ethers (see Patent Document 3), iv) a photosensitive composition containing thioxanthones (see Patent Document 4), v) containing a biimidazole compound, and A pattern forming material containing acridone as a sensitizer (see Patent Document 5) has been proposed.
In general, the pattern forming material is exposed using a mask. However, in recent years, a digital micromirror device (DMD) or the like is used from the viewpoint of productivity and resolution. A maskless exposure apparatus using a conventional laser beam has been actively studied.

  In order to obtain the permanent pattern with high definition and efficiency, a high-sensitivity photosensitive layer has been developed in recent years that uses a 395 nm to 415 nm blue-ultraviolet laser and can be efficiently exposed with low energy. However, since the pattern forming material has higher sensitivity of the photosensitive layer than the conventional pattern forming material, it easily causes a photoreaction to the safelight, and the pattern forming material under the safelight for a long time. In the case of handling the photosensitive material, there is a problem that when the light of 395 nm to 415 nm is exposed later, the problem of so-called optical fogging that the sensitivity and the obtained resist line width are increased easily occurs.

On the other hand, photoresists for printed circuit board manufacturing are being switched from liquid resists to dry films for reasons such as high sensitivity, high resolution, and ease of handling. Even now, liquid resists are mostly used, and dry film formation is delayed.
As a cause thereof, carboxylic acid group-containing resin for alkali development treatment, epoxy resin is an essential component in order to realize the heat resistance, hardness, substrate adhesion, etc. of the obtained solder resist cured film, Since both are highly reactive, the reaction proceeds due to heat, etc. during the drying process or storage, and the developability is lowered, which limits the storage stability of the solder resist film. .
Further, it has been known that a dry film for pattern formation containing no epoxy compound is sensitized by 10% or more of the initial value during storage, and further stabilization has been desired.

  As described above, when applying to a blue-violet laser exposure system capable of maskless exposure, in order to realize a highly sensitive pattern forming material, improvement in light stability and thermal stability with respect to safelight light is a major issue. one of.

  Therefore, it has high sensitivity to blue-ultraviolet lasers, is excellent in light stability and thermal stability under yellow safety lights, has extremely high storage stability, and has high definition patterns such as wiring patterns and solder resist patterns. In addition, a pattern forming material that can be efficiently formed, a pattern forming apparatus including the pattern forming material, and a pattern forming method using the pattern forming material have not been provided yet, and further improvement and development are desired. This is the current situation.

JP-A-11-316457 JP 2000-214584 A JP 2001-302871 A JP 2003-280193 A JP-A-2005-107191

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is highly sensitive to a blue-ultraviolet laser, excellent in light stability and thermal stability under a yellow safety light, extremely high in storage stability, and has a wiring pattern and permanent pattern (protective film, A photosensitive composition capable of efficiently forming a pattern such as an interlayer insulating film and a solder resist pattern with high definition and efficiency, a pattern forming material and a photosensitive laminate obtained by laminating the photosensitive composition, and a pattern forming apparatus And a pattern forming method.

Means for solving the problems are as follows. That is,
<1> At least a binder, a polymerizable compound, and a photopolymerization initiation system compound, wherein the photopolymerization initiation system compound includes an acridine derivative represented by the following general formula (I) and an onium compound. It is a photosensitive composition.

In the general formula (I), A is an oxygen atom, represents one of a sulfur atom, and ^{NR 10, R 1, R 2} , R 3, R 4, R 5, R 6, R 7, R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent, and groups adjacent to each other may be bonded to form a ring. The monovalent substituent may further have a substituent.
The photosensitive composition according to <1> has high sensitivity to a blue ultraviolet laser, is excellent in light stability and thermal stability under a yellow safety light, and has extremely high storage stability. By using the photosensitive layer formed of such a photosensitive composition, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high definition pattern.
<2> The photosensitive composition according to <1>, wherein the acridine derivative is an acridone compound represented by the following general formula (II).
However, in said general formula (II), R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R <^7> , and R <^8> are each independently a hydrogen atom and a monovalent substituent. R ⁹ represents an alkyl group. Adjacent groups may combine to form a ring. The monovalent substituent may further have a substituent.
<3> The photosensitive composition according to any one of <1> to <2>, wherein the onium compound is at least one selected from an iodonium compound, a sulfonium compound, and a pyridinium compound.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the pyridinium compound is represented by the following general formula (a).

However, in said general formula (a), R <^15> , R <^16> , R <^17> , R <^18> , R <^19> , and R < ²⁰ > represent the organic group which may mutually be same or different, Among these, At least one represents an organic group represented by the following general formula (a-1). X ^m− represents an m-valent anion, and m represents an integer of 1 to 6.
However, in General Formula (a-1), R ²¹ , R ²² , and R ²³ represent an organic group that may be the same as or different from each other, and L is a divalent that may contain a hetero atom. Represents a linking group.
<5> The photosensitive composition according to any one of <1> to <4>, comprising a hydrogen donor compound.
<6> The hydrogen donor compound is 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -2-butan-1-one, 1-phenyl-2-mercapto-1,3-benz Imidazole, N-phenylglycine, 4,4′-bis (diethylamino) benzophenone, leucocrystal violet, 2-dimethylamino-2-methyl-1- (4-methoxyphenyl) propan-1-one-O-allyloxime, And tetra (n-butyl) ammonium-n-butyltriphenylborate. The photosensitive composition according to <5>.

<7> The photosensitive composition according to any one of <1> to <6>, including a thermal crosslinking agent and a thermosetting accelerator, wherein the binder includes an alkali-soluble photocrosslinkable resin.
<8> The photosensitive composition according to any one of <1> to <6>, wherein the binder includes a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative. It is.
<9> The photosensitive composition according to any one of <1> to <6> and <8>, wherein the binder has a glass transition temperature (Tg) of 80 ° C. or higher.
<10> The photosensitive composition according to any one of <1> to <7>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acryl group.
<11> The photosensitive composition according to any one of <1> to <6> and <8> to <9>, wherein the polymerizable compound includes a monomer having at least one of a urethane group and an aryl group. .
<12> The <7> and <7>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 10>. The photosensitive composition according to any one of 10>.
<13> The photosensitive composition according to any one of <7>, <10>, and <12>, which contains an inorganic filler.
<14> The photosensitive composition according to any one of <1> to <13>, including a colorant.
<15> Binder 15 to 70% by mass, polymerizable compound 5 to 75% by mass, thermal crosslinking agent 2 to 50% by mass, thermosetting accelerator 0.01 to 20% by mass, inorganic filler 5 to 75% by mass, The photosensitive composition according to any one of <7>, <10>, and <12> to <14>, comprising 0.1 to 10% by mass of a colorant and a solvent.
<16> The binder according to any one of <7>, <10>, <12> and <14>, containing 10 to 90% by mass of a binder and 5 to 90% by mass of a polymerizable compound. It is a photosensitive composition.

<17> A pattern forming material comprising at least a support and a photosensitive layer comprising the photosensitive composition according to any one of <1> to <16> on the support.
<18> The pattern forming material according to <17>, wherein the support has a cushion layer and a photosensitive layer in this order.
<19> The pattern forming material according to any one of <17> to <18>, wherein the support includes a synthetic resin and is transparent.
<20> The pattern forming material according to any one of <17> to <19>, wherein the support has a long shape.
<21> The pattern forming material according to any one of <17> to <20>, which is long and wound in a roll shape.
<22> The pattern forming material according to any one of <17> to <21>, wherein the pattern forming material has a protective film on the photosensitive layer.

<23> A photosensitive laminate comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <16> on a substrate.
<24> The photosensitive laminate according to <23>, wherein the photosensitive layer is formed of the pattern forming material according to any one of <17> to <22>.
<25> The photosensitive laminate according to any one of <23> to <24>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<26> The photosensitive laminate according to any one of <23> to <25> is provided,
A pattern forming apparatus comprising: a light irradiating unit capable of irradiating light; and a light modulating unit configured to modulate light from the light irradiating unit and to expose a photosensitive layer in the photosensitive laminate. It is. In the pattern forming apparatus according to <26>, the light irradiation unit irradiates light toward the light modulation unit. The light modulation unit modulates light received from the light irradiation unit. The light modulated by the light modulator is exposed to the photosensitive layer. For example, when the photosensitive layer is subsequently developed, a high-definition pattern is formed.
<27> The light modulation means further includes pattern signal generation means for generating a control signal based on the pattern information to be formed, and the control signal generated by the pattern signal generation means is emitted from the light irradiation means. It is a pattern formation apparatus as described in said <26> modulated according to. In the pattern forming apparatus according to <27>, since the light modulation unit includes the pattern signal generation unit, the light emitted from the light irradiation unit corresponds to the control signal generated by the pattern signal generation unit. Modulated.
<28> The light modulation means has n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The pattern forming apparatus according to any one of <26> to <27>, which can be controlled according to pattern information. In the pattern forming apparatus according to <28>, an arbitrary less than n pixel portions arranged in succession among n pixel portions in the light modulation unit are controlled according to pattern information. Thereby, the light from the light irradiation means is modulated at high speed.
<29> The pattern forming apparatus according to any one of <26> to <28>, wherein the light modulation unit is a spatial light modulation element.
<30> The pattern forming apparatus according to <29>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<31> The pattern forming apparatus according to any one of <28> to <30>, wherein the picture element portion is a micromirror.
<32> The pattern forming apparatus according to any one of <26> to <31>, wherein the light irradiation unit can synthesize and irradiate two or more lights. In the pattern forming apparatus according to <32>, since the light irradiation unit can synthesize and irradiate two or more lights, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<33> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams emitted from the plurality of lasers and couples the laser beams to the multimode optical fiber. The pattern forming apparatus according to any one of <26> to <32>. In the pattern forming apparatus according to <33>, the light irradiation unit can condense the laser beams irradiated from the plurality of lasers by the collective optical system and couple the laser beams to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<34> A pattern forming method comprising at least exposing the photosensitive layer in the photosensitive laminate according to any one of <23> to <25>.
<35> After the photosensitive layer in the pattern forming material according to any one of <17> to <22> is laminated on the surface of the base material under at least one of heating and pressurization, The pattern forming method according to <34>, wherein the exposure is performed.
<36> The pattern forming method according to any one of <34> to <35>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm.
<37> The pattern forming method according to any one of <34> to <36>, wherein the exposure is performed imagewise based on pattern information to be formed.

<38> The photosensitive layer has light irradiation means and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel parts that receive and emit light from the light irradiation means. An exposure head provided with a light modulation means capable of controlling the picture element unit according to pattern information, wherein the column direction of the picture element part is a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using an exposure head arranged to form
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The pattern forming method according to <34> to <37>, wherein the exposure head is moved relative to the photosensitive layer in a scanning direction. In the pattern forming method according to <38>, the exposure head is subjected to N-exposure (where N is a natural number of 2 or more) among the usable pixel parts by the used pixel part specifying unit. The pixel part to be used is specified, and the pixel part is controlled by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in exposure. By performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction, the exposure head is formed on the exposed surface of the photosensitive layer due to a shift in the mounting position or mounting angle of the exposure head. Variations in the resolution of the pattern and unevenness in density are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<39> The exposure is performed by a plurality of exposure heads, and the used drawing element specifying means is related to the exposure of the joint area between the heads which is the overlapping exposure area on the exposed surface formed by the plurality of exposure heads. The pattern forming method according to <38>, wherein, among the element parts, the image element part used for realizing N double exposure in the inter-head connection region is designated. In the pattern forming method according to <39>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designation unit is an overlapped exposure region on an exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in the exposure of the head-to-head connection area, the picture element part used for realizing the N-fold exposure in the head-to-head connection area is designated, so that the mounting position and mounting of the exposure head Variations in resolution and density unevenness of the pattern formed in the connecting area between the heads on the exposed surface of the photosensitive layer due to the angle shift are leveled. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<40> The exposure is performed by a plurality of exposure heads, and the used picture element specifying means is involved in exposure other than the inter-head connection region, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. The pattern forming method according to <39>, wherein the image element portion used for realizing N double exposure in an area other than the inter-head connection area among the image element parts is designated. In the pattern forming method according to <40>, the exposure is performed by a plurality of exposure heads, and the used pixel portion designating unit is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads. Of the picture element parts involved in exposure other than the inter-head connection area, the attachment position of the exposure head is specified by designating the picture element part used for realizing N-fold exposure in areas other than the inter-head connection area. Variations in the resolution and density unevenness of the pattern formed in areas other than the head-to-head connection area on the exposed surface of the photosensitive layer due to the mounting angle deviation are equalized. As a result, the photosensitive layer is exposed with high definition, and then the photosensitive layer is developed to form a high-definition pattern.
<41> When the set inclination angle θ is N, the number N of the multiple exposures, the number s of the pixel portions in the column direction, the interval p in the column direction of the pixel portions, and the exposure head tilted. the relative row direction pitch δ of pixel parts in the direction perpendicular to the scanning direction, the following equation with respect to theta _ideal satisfying spsinθ _ideal ≧ Nδ, which is set so as to satisfy the relation of θ ≧ θ _ideal <38> to <40>.
<42> The pattern forming method according to any one of <38> to <41>, wherein N in N-fold exposure is a natural number of 3 or more. In the pattern forming method according to <42>, multiple drawing is performed when N in N double exposure is a natural number of 3 or more. As a result, due to the effect of filling, variations in the resolution and density unevenness of the pattern formed on the exposed surface of the photosensitive layer due to a shift in the mounting position and mounting angle of the exposure head are more precisely leveled.

<43> Use pixel part designation means
A light spot position detecting means for detecting a light spot position on a surface to be exposed as a pixel unit generated by a picture element unit and constituting an exposure area on the surface to be exposed;
<38> to <42>, further comprising: a pixel part selection unit that selects a pixel part to be used for realizing N double exposure based on a detection result by the light spot position detection unit. This is a pattern forming method.
<44> The pattern forming method according to any one of <38> to <43>, wherein the used pixel part specifying unit specifies the used pixel part used for realizing the N-exposure in a line unit. is there.

<45> The light spot position detecting means, based on the detected at least two light spot positions, the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. The inclination angle θ ′ is specified, and the drawing element selection means selects the drawing element part so as to absorb the error between the actual inclination angle θ ′ and the set inclination angle θ. The pattern forming method according to any one of the above.
<46> The average inclination angle θ ′ is an average value, a median value, and a plurality of actual inclination angles formed by the row direction of the light spots on the surface to be exposed and the scanning direction of the exposure head when the exposure head is inclined. The pattern forming method according to <45>, wherein the pattern forming method is one of a maximum value and a minimum value.
<47> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m <43> to <46> for selecting the pixel part from the first line to the T-th line in a line element (where m represents a natural number of 2 or more) arranged as a used pixel part The pattern forming method according to any one of the above.
<48> The pixel part selection means derives a natural number T close to t that satisfies the relationship of ttan θ ′ = N (where N represents N of N double exposure numbers) based on the actual inclination angle θ ′, and m In the picture element part arranged in a row (where m represents a natural number of 2 or more), the picture element part from line (T + 1) to m-th line is specified as an unused picture element part, and the unused picture element part is specified. The pattern forming method according to any one of <43> to <46>, wherein the pixel part excluding the element part is selected as a use pixel part.

<49> In a region including at least an overlapped exposure region on an exposed surface formed by a plurality of pixel part rows, the pixel part selection unit,
(1) Means for selecting a used pixel portion so that a total area of an overexposed region and an underexposed region is minimized with respect to an ideal N-fold exposure;
(2) Means for selecting a pixel part to be used so that the number of pixel units in an overexposed area and the number of pixel units in an underexposed area are equal to each other with respect to an ideal N double exposure;
(3) Means for selecting a pixel part to be used so that the area of an overexposed area is minimized and an underexposed area does not occur with respect to an ideal N double exposure, and (4) Ideal From the above <43>, which is one of means for selecting a pixel part to be used so that the area of an underexposed area is minimized and an overexposed area does not occur with respect to typical N double exposure <48>. The pattern forming method according to <48>.
<50> In the connection region between the heads, which is an overlapping exposure region on the exposed surface formed by the plurality of exposure heads,
(1) With respect to the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connection region, the total area of the overexposed region and the underexposed region is minimized. Means for identifying a used pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
(2) Involvement in the exposure of the head-to-head connecting region so that the number of pixel units in the overexposed region and the number of pixel units in the underexposed region are equal to the ideal N-double exposure. Means for identifying an unused pixel part from the pixel part to be selected, and selecting the pixel part excluding the unused pixel part as a used pixel part;
(3) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the overexposed region is minimized and the underexposed region is not generated. A means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part; and
(4) For the ideal N-multiple exposure, from the pixel part involved in the exposure of the inter-head connecting region, the area of the underexposed region is minimized and the region that is overexposed is not generated. , Means for identifying an unused pixel part and selecting the pixel part excluding the unused pixel part as a used pixel part;
The pattern forming method according to any one of <43> to <49>.
<51> The pattern forming method according to <50>, wherein the unused pixel parts are specified in units of rows.

<52> In order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N (n-1) pixel part columns for N multiple exposures The pattern forming method according to any one of <38> to <51>, wherein the reference exposure is performed using only the picture element portion that constitutes. In the pattern forming method according to <52>, in order to specify the used pixel part in the used pixel part specifying unit, among the usable pixel parts, N of N double exposures (N -1) Reference exposure is performed using only the pixel part constituting the pixel part column for each column, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.
<53> In order to specify the used pixel part in the used pixel part specifying means, among the usable pixel parts, for each N-exposure N, a pixel part line is formed every 1 / N lines. The pattern forming method according to any one of <38> to <52>, wherein the reference exposure is performed using only the pixel part. In the pattern forming method according to <53>, in order to designate a used pixel part in the used pixel part designating unit, among the usable picture element parts, 1 / Reference exposure is performed using only the pixel part constituting the pixel part column for every N rows, and a simple pattern of substantially single drawing is obtained. As a result, the picture element portion in the head-to-head connection region is easily specified.

<54> From the above <38> to <53>, the used pixel part designation unit includes a slit and a photodetector as a light spot position detection unit, and an arithmetic unit connected to the photodetector as a pixel unit selection unit. The pattern forming method according to any one of the above.
<55> The pattern forming method according to any one of <38> to <54>, wherein N in N-exposure exposure is a natural number of 3 or more and 7 or less.
<56> Any one of <38> to <55>, wherein the pattern information is converted so that a dimension of a predetermined part of the pattern represented by the pattern information matches a dimension of a corresponding part that can be realized by the designated used pixel part The pattern forming method according to claim 1.

<57> The pattern forming method according to any one of <34> to <56>, wherein the photosensitive layer is developed after the exposure.
<58> The pattern forming method according to <57>, wherein after the development, the photosensitive layer is subjected to a curing treatment.
<59> The pattern forming method according to <58>, wherein the curing process is at least one of an entire surface exposure process and an entire surface heat treatment performed at 120 to 200 ° C. In the pattern forming method according to <58>, curing of the resin in the photosensitive composition is promoted in the overall exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.
<60> The pattern forming method according to <59>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.

  According to the present invention, conventional problems can be solved, high sensitivity to a blue ultraviolet laser, excellent light stability and thermal stability under a yellow safety light, extremely high storage stability, A photosensitive composition capable of forming a wiring pattern and a permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern) with high definition and efficiency, a pattern forming material obtained by laminating the photosensitive composition, and A photosensitive laminate, a pattern forming apparatus, and a pattern forming method can be provided.

  The present invention is a photosensitive composition, a pattern forming material and a photosensitive laminate obtained by laminating a photosensitive layer made of the photosensitive composition, a pattern forming apparatus, and a pattern forming method, which will be described in order below.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least a binder, a polymerizable compound, and a photopolymerization initiation system compound, and other components appropriately selected as necessary.

  Examples of the photosensitive composition include a photosensitive composition for solder resist used for forming a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, and an etching resist used for forming a wiring pattern and the like. A photosensitive composition.

<Photopolymerization initiation compound>
The photopolymerization initiating compound includes an acridine derivative represented by the following general formula (I) and an onium compound, and further preferably includes a hydrogen donor compound.

-Acridine derivative-
The acridine derivative is a compound represented by the following general formula (I).

In the general formula (I), A represents an oxygen atom, a sulfur atom, or NR ¹⁰ .

In the general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom and one Any one of the valent substituents, and groups adjacent to each other may be bonded to form a ring. The monovalent substituent may further have a substituent.

  In the general formula (I), as the monovalent substituent, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a trifluoromethyl group, a benzyl group, a sulfopropyl group, Diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group, ethoxyethyl group, ethylthioethyl group, phenoxyethyl group, carbamoylethyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc.) Alkenyl group (for example, allyl group, styryl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-carboxyphenyl group, 3,5-dicarboxyphenyl group, m-sulfophenyl group, p-acetamidophenyl group) 3-caprylamidophenyl group, p-sulfamoylpheny Group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl group, p-cyanophenyl group, pN-methylureidophenyl group, m-fluorophenyl Group, p-tolyl group, m-tolyl group, etc.), heterocyclic group (for example, pyridyl group, 5-methyl-2-pyridyl group, thienyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, fluorine atom) Etc.), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, nitro group, alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-phenylethoxy group, etc.) ), Aryloxy group (for example, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, α-naphthoxy group, etc.), acyl (For example, acetyl group, benzoyl group, etc.), acylamino group (for example, acetylamino group, caproylamino group, etc.), sulfonyl group (for example, methanesulfonyl group, benzenesulfonyl group, etc.), sulfonylamino group (for example, methanesulfonyl group) Amino group, benzenesulfonylamino group, etc.), amino group (e.g., diethylamino group, hydroxyamino group, etc.), alkylthio group or arylthio group (e.g., methylthio group, carboxyethyl group, sulfobutylthio group, phenylthio group, etc.), alkoxy Examples thereof include a carbonyl group (for example, methoxycarbonyl group), an aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like. These may further have a substituent.

In the general formula (I), R ⁹ is preferably an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an acyl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or an aryloxycarbonyl group. An aryl group, an alkenyl group, and an acyl group are particularly preferable. These may further have a substituent.

In the general formula (I), R ¹⁰ is preferably an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an acyl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or an aryloxycarbonyl group. An alkoxy group, an aryloxy group, an acyl group, an alkylthio group, and an alkoxycarbonyl group are particularly preferable. These may further have a substituent.

The acridine derivative is preferably an acridone compound represented by the following general formula (II).

In the general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a monovalent substituent. Represents

In the general formula (II), R ⁹ represents an alkyl group. Adjacent groups may combine to form a ring. The monovalent substituent may further have a substituent.

  Specific examples of the acridone compound include N-methylacridone, 1-chloro-N-methylacridone, 1-bromo-N-methylacridone, 2-chloro-N-methylacridone, and 3-chloro. -N-methylacridone, 4-chloro-N-methylacridone, 2-chloro-N- (2-phenoxyethyl) acridone, 3-chloro-N- (n-butyl) acridone, 2,3-dichloro- N-methylacridone, 2,6-dichloro-N-methylacridone, 2-chloro-6-bromo-N-methylacridone, 2-chloro-N-ethylacridone, 2-chloro-N- (n -Butyl) acridone, 2,6-dichloro-N- (n-butyl) acridone, 2,7-dichloro-N- (n-butyl) acridone, 2,7-dibromo-N- (n-butyl) actyl Don, 2-bromo-N-octylacridone, 2-chloro-N-allylacridone, 3-chloro-N-benzylacridone, 2,3-diethoxy-N- (n-butyl) acridone, 2-phenyl -N- (n-butyl) acridone, 2-ethoxycarbonyl-N- (n-butyl) acridone, N-phenylacridone, 2-phenoxycarbonyl-N- (n-butyl) acridone, 2-cyano-N- (N-butyl) acridone, 2-methylsulfonyl-N- (n-butyl) acridone, 2,7-bis (ethoxycarbonyl) -N- (n-butyl) acridone, N- (n-butyl) -1, 2-benzacridone, N- (n-butyl) -2,3-benzacridone, acridone, 2- (N, N-diethylamino) -N′-ethylacridone, 3, -Bis (N, N-diethylamino) -N'-ethylacridone, 2-phenoxycarbonyl-N- (2-methoxyethyl) acridone, 2,4,5,7-tetrachloro-N-methylacridone, N -Ethoxycarbonylmethylacridone, 3-trifluoromethyl-N- (n-hexyl) acridone, 4,5-dichloroacridone, N- (n-butyl) -3,4-benzacridone, 2-benzoyl- N- (n-hexyl) acridone, 2-phenoxy-N- (2-hydroxyethyl) acridone, 2-phenylthio-N-ethylacridone, 2-chloro-N-propargylacridone, 3-hydroxycarbonyl-N- (N-butyl) acridone, 2,3-bis (phenoxycarbonyl) -N- (n-butyl) acridone, 2,4,5,7 -Tetrabromo-N-methylacridone, N-methylthioacridone, Nn-butylthioacridone, Nn-butyl-2-methoxythioacridone, Nn-butyl-2-chlorothioacridone, Nn-butyl-2,7-dichlorothioacridone, N-ethyl-3-diethylaminothioacridone, Nn-butyl-2-benzoylthioacridone, N- (n-butyl) -1,2 -Benzothioacridone, N- (2-diethylaminoethyl) -2-bromothioacridone, N-methyl-2,3-diethoxythioacridone, 10-n-butyl-9,10-dihydroacridine-9 -Ilidene-ethylamine, 10-n-hexyl-9,10-dihydroacridine-9-ylidene-benzylamine, 10- (2-methoxyethyl) -9, 0-dihydroacridine-9-ylidene-n-butylamine, 10-ethyl-2-benzoyl-9,10-dihydroacridine-9-ylidene-ethoxyamine, 10-n-butyl-2-methyl-9,10-dihydro Acridine-9-ylidene-aniline, 10-n-hexyl-3-chloro-9,10-dihydroacridine-9-ylidene-propanoylamide, 10-ethyl-9,10-dihydroacridine-9-ylidene-benzoyloxy Amine, 10-methyl-9,10-dihydroacridine-9-ylidene-p-toluenesulfonyloxyamine, 10-ethyl-2-phenoxycarbonyl-9,10-dihydroacridine-9-ylidene-phenylcarbamoyloxyamine, 10 -Phenyl-9,10-dihydroacridine 9-ylidene - such as ethoxycarbonyloxy amines preferably Among them, 2-chloro-N-(n-butyl) acridone and N- methyl acridone and the like more preferred.

  As content of the acridine derivative in the said photosensitive composition, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

-Onium compounds-
The onium compound is not particularly limited as long as it is neutral, and can be appropriately selected from an electron-accepting radical generator and an electron-donating active radical generator. This is preferable because it provides high sensitivity.

Here, in the radical generator, neutral means neutral (pH = 6.4 to 7.4) when the active radical generator is dissolved in water or a solution of a solvent miscible with water. Those that do not contain basic groups such as amino groups, carboxylic acid groups, sulfonic acid groups, etc. in the molecule, and those that exist, It is appropriately selected from those that are neutralized by the binding of or by binding to other acidic molecules or basic molecules.
From such a viewpoint, the onium compound is preferably at least one selected from iodonium compounds, sulfonium compounds, and pyridium compounds.
Examples of the onium compounds include N, P, As, Sb, Bi, O, S, Se, Te, and I, which are elements of Group 15 (5B), 16 (6B), and 17 (7B) of the periodic table. An aromatic onium salt having at least one of them is included. Examples of such aromatic onium salts include compounds shown in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, and Japanese Patent Publication No. 52-14279.

  As said iodonium compound, the compound represented by the following general formula (III) is mentioned suitably, for example.

However, in the general formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, and an aryl having 12 or less carbon atoms. An oxy group is mentioned.
Z ¹¹⁻ represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and includes a perchlorate ion, a hexafluorophosphate ion, Aryl sulfonate ions are preferred.

Preferable specific examples of the iodonium compound represented by the general formula (III) include the following compounds (III-1) to (III-12).
(III-1) 4-Tolyl-4′-iso-butylphenyliodonium-hexafluorophosphate (III-2) di (4-n-dodecylphenyl) iodonium-hexafluoroantimonate (III-3) di (p -Fluorophenyl) iodonium-trifluoromethanesulfonate (III-4) Di (p-tert-butylphenyl) iodonium-hexafluorophosphate (III-5) Di (p-tert-pentylphenyl) iodonium-hexafluorophosphate (III-6) Di (p-tert-pentylphenyl) iodonium-perchlorate (III-7) Di (p-tert-pentylphenyl) iodonium-p-toluenesulfonate (III-8) Di (p-tert-pentyl) Phenyl) yo Ni-Mesitylsulfonate (III-9) Di (p-tert-pentylphenyl) iodonium-2,4,6-triisopropylbenzenesulfonate (III-10) Di (p-tert-pentylphenyl) iodonium-perfluoro Benzenesulfonate (III-11) Phenyl pn-hexyloxyphenyliodonium-hexafluorophosphate (III-12) pn-hexylphenyl pn-hexylphenyliodonium-p-toluenesulfonate

  As said sulfonium compound, the compound represented by the following general formula (IV) is mentioned suitably, for example.

In the general formula ^{(IV), R 21, R} 22, and R ²³ may each have the same or different and carbide having 20 or less carbon atoms which may have a substituent Represents a hydrogen group. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, and an aryloxy group having 12 or less carbon atoms. Z ^31- represents the same meaning as Z ^11- .

Preferable specific examples of the sulfonium compound represented by the general formula (IV) include the following compounds (IV-1) to (IV-21).
(IV-1) 4-phenylthiophenyldiphenylsulfonium-hexafluorophosphate (IV-2) triphenylsulfonium-perfluorobenzenesulfonate (IV-3) triphenylsulfonium-2,4,6-triisopropylbenzenesulfonate (IV-4) Triphenylsulfonium-trifluoromethanesulfonate (IV-5) Tri (p-isopropylphenyl) sulfonium-p-toluenesulfonate (IV-6) Dimethylphenacylsulfonium-tetrakis (pentafluorophenyl) borate ( IV-7) Dimethyl β-naphthoylmethylsulfonium-hexafluorophosphate (IV-8) Phenacyltetramethylenesulfonium-hexafluorophosphate (IV-9) 4-nitroph Nasyltetramethylenesulfonium-hexafluoroarsenate (IV-10) 4-bromophenacyltetramethylenesulfonium-hexafluoroantimonate (IV-11) 4-phenylphenacyltetramethylenesulfonium-hexachloroferrate (IV-12) β -Naphthoylmethyltetramethylenesulfonium-hexachlorostannate (IV-13) Triphenylsulfonium-hexachloroantimonate (IV-14) Phenyldibenzothiophenium-tetrafluoroborate (IV-15) 4,4'-bis ( Bisphenylsulfonio) phenyl sulfide bishexafluorophosphate (IV-16) 2,4-diethyl-7-di (4-fluorophenyl) sulfoniothioxanthone-hexafluoroa Timonate (IV-17) 1-chloro-4-n-propoxy-7-di (4-tolyl) sulfoniothioxanthone-hexafluoroantimonate (IV-18) 2-isopropyl-7-diphenylsulfoniothioxanthone-hexafluoro Phosphate (IV-19) 2,4-Diethyl-7-bis (4-β-hydroxyethoxyphenyl) sulfoniothioxanthone-hexafluorophosphate (IV-20) Diphenyl-4- (4-benzoylphenylthio) phenyl Sulfonium hexafluorophosphate (IV-21) α- (methyl-β-naphthylsulfonia) acetic acid methyl hexafluorophosphate

  As said pyridinium compound, the compound represented by the following general formula (V) is mentioned suitably, for example.

However, in said general formula (V), R < ^{31 >} , R ^{< 32>} , R ^<33> , R ^<34> , R ^<35> , and R ^<36 > may represent the same or different organic group, respectively, At least one of them represents an organic group represented by the following general formula (Vi). Z ^31m- represents an m-valent anion, and m represents an integer of 1-6.
However, in general formula (Vi), R ^<37> , R ^<38> and R ^<39 > may represent the same or different organic group, respectively, and L is a bivalent coupling | bonding containing a hetero atom. Represents a group.

Preferable specific examples of the pyridinium compound represented by the general formula (V) include the following compounds (V-1) to (V-72).
(V-1) 1-benzyl-4-benzoyloxymethylpyridinium-hexafluorophosphate (V-2) 4-benzoyloxymethylpyridine-hydrochloride (V-3) 1-methyl-4-benzoyloxymethylpyridinium- p-toluenesulfonate (V-4) 1-n-heptyl-4-benzoyloxymethylpyridinium-p-toluenesulfonate (V-5) 1- (4-nitrophenyl) -4-benzoyloxymethylpyridinium-tetra Fluoroborate (V-6) 1- (1-propenyl) -4- (4-methoxybenzoyloxymethyl) pyridinium-tetrafluoroborate (V-7) 1- (1-propynyl) -4- (4- Methoxybenzoyloxymethyl) pyridinium-hexafluorophosphate (V-8) 1 n-Heptyl-4- (4-trifluoromethylbenzoyloxymethyl) pyridinium-tetrafluoroborate (V-9) 1-n-octyl-4- (4-dimethylaminobenzoyloxymethyl) pyridinium-p-toluenesulfo Nert (V-10) 1-benzyl-4- (α-phenylthioacetyloxymethyl) pyridinium-hexafluorophosphate (V-11) 1-benzyl-4- (α-phenoxyacetyloxymethyl) pyridinium-hexafluoro Phosphate (V-12) 1-benzyl-4- [α- (N-methyl-N-phenylamino) acetyloxymethyl] pyridinium-tetrafluoroborate (V-13) 1- (4-trifluoromethylbenzyl) ) -4- (α-Phenylthioacetyloxymethyl) pyridy Um-tetrafluoroborate (V-14) 1- (4-trifluoromethylbenzyl) -3,5-dimethyl-4- (α-phenylthioacetyloxymethyl) pyridinium-tetrafluoroborate (V-15) 1-Benzyl-2-chloro-4- [α- (2-methylphenoxy) acetyloxymethyl] pyridinium-hexafluoroantimonate (V-16) 1-n-heptyl-4-tert-butoxycarbonyloxymethylpyridinium- p-Toluenesulfonate

(V-17) 1-heptyl-4-pivaloyloxymethylpyridinium-p-toluenesulfonate (V-18) 1-benzyl-4- (4-tert-butylbenzoyl) pyridinium-tetrafluoroborate (V -19) 1-n-heptyl-4- (N-methylaminocarboxymethyl) pyridinium-p-toluenesulfonate (V-20) 1-n-heptyl-3-benzoyloxymethylpyridinium-p-toluenesulfonate ( V-21) 1-n-heptyl-3-pivaloyloxymethylpyridinium-hexafluorophosphate (V-22) 1-benzyl-3-benzoyloxymethylpyridinium-tetrafluoroborate (V-23) 1- Benzyl-3- (α-phenylthioacetyloxymethyl) pyridinium-he Safluorophosphate (V-24) 1-methyl-3-benzoyloxymethylpyridinium-p-toluenesulfonate (V-25) 1-n-heptyl-2,6-dimethyl-3-benzoyloxymethylpyridinium-hexa Fluorophosphate (V-26) 1-n-heptyl-2-chloro-3-benzoyloxymethylpyridinium-tetrafluoroborate (V-27) 1- (4-tert-butylbenzyl) -2- (α- Phenylthioacetyloxymethyl) pyridinium-hexafluorophosphate (V-28) 1- (4-tert-butylbenzyl) -2- (α-phenylthioacetyloxymethyl) -3-tert-butyl-6-chloropyridinium -Bromide (V-29) 1-benzyl-2- (crotonoyloxy) Til) pyridinium-hexafluorophosphate (V-30) 1-benzyl-2- (but-1-noyloxymethyl) pyridinium-tetrafluoroborate (V-31) 1-methyl-2-benzoyloxymethylpyridinium- Perchlorate (V-32) 1-benzyl-2- (4-nitrobenzoyloxymethyl) pyridinium-hexafluoroantimonate (V-33) 1-methyl-2-hexanoyloxymethyl-3-acetylpyridinium-perchlorate (V -34) 1-n-heptyl-2-cyclopropanecarbonyloxymethylpyridinium-hexafluoroantimonate (V-35) 1-methyl-2,6-bis (benzoyloxymethyl) pyridinium-p-toluenesulfonate (V -36) 1-n-Hep Le-2,3-bis (benzoyloxy-methyl) pyridinium - hexafluorophosphate

(V-37) 1-phenyl-2,4-bis (benzoyloxymethyl) pyridinium-hexafluorophosphate (V-38) 1-benzyl-4- [2- (α-trimethylsilylacetyloxy) ethyl] pyridinium- Tetrafluoroborate (V-39) 1-n-heptyl-3,5-dimethyl-4 (2-benzoyloxyethyl) pyridinium-p-toluenesulfonate (V-40) 1-benzyl-2- (1- Benzoyloxyisopropyl) pyridinium-tetrafluoroborate

(V-41)
(V-42)
(V-43)
(V-44)

(V-45) 1-benzyl-4-benzoylformyloxymethylpyridinium-hexafluorophosphate (V-46) 1-benzyl-2-chloro-4-benzoylformyloxymethylpyridinium-p-toluenesulfonate (V- 47) 1-Benzyl-3-methyl-4-benzoylformyloxymethylpyridinium-tetrafluoroborate (V-48) 1-n-heptyl-4-acetylformyloxymethylpyridinium-hexafluorophosphate (V-49) 1-n-heptyl-4-benzoylformyloxymethylpyridinium-hexafluorophosphate (V-50) 1-methyl-4-octanoylformyloxymethylpyridinium-p-toluenesulfonate (V-51) 1-n- Heptyl-3-benzo Ilformyloxymethylpyridinium-hexafluorophosphate (V-52) 1-benzyl-2-methyl-5-benzoylformyloxymethylpyridinium-hexafluorophosphate (V-53) 1-benzyl-2-benzoylformyloxymethyl Pyridinium-hexafluorophosphate (V-54) 1- (4-trifluoromethylbenzyl) -4-benzoylformyloxymethylpyridinium-tetrafluoroborate (V-55) 1- (4-trifluoromethylbenzyl)- 2-Benzoylformyloxymethylpyridinium-hexafluorophosphate (V-56) 1-benzyl-4- (4-methoxybenzoylformyloxymethyl) pyridinium-hexafluorophosphate (V-57) 1-Benzene -4- (4-Methoxybenzoylformyloxymethyl) pyridinium-tetrafluoroborate (V-58) 1-benzyl-4-phenoxysulfonylmethylpyridinium-hexafluorophosphate (V-59) 1-benzyl-4-benzyl Oxysulfonylmethylpyridinium-p-toluenesulfonate (V-60) 1-n-heptyl-4-phenoxysulfonylmethylpyridinium-hexafluorophosphate (V-61) 1-n-heptyl-4-n-pentyloxysulfonyl Methylpyridinium-hexafluorophosphate

(V-62) 1- (4-trifluoromethylbenzyl) -4-phenoxysulfonylmethylpyridinium-p-toluenesulfonate (V-63) 1-benzyl-4-acetylaminomethylpyridinium-hexafluorophosphate (V -64) 1-benzyl-4-benzoylaminomethylpyridinium-hexafluorophosphate (V-65) 4- (N-methyl-benzoylaminomethyl) pyridine-p-toluenesulfonate (V-66) 1-n -Heptyl-4-acetylaminomethylpyridinium-tetrafluoroborate (V-67) 1-n-heptyl-4- (2-methylpropanoyl) aminomethylpyridinium-hexafluorophosphate (V-68) 1-benzyl -4- (Nn-butylaminocarbonylaminomethyl) Til) pyridinium-hexafluorophosphate (V-69) 1-benzyl-4- (N-methyl-N-phenylaminocarbonyl-N′-methylaminomethyl) pyridinium-hexafluorophosphate (V-70) 1- n-heptyl-4- (N-phenylaminocarbonylaminomethyl) pyridinium-p-toluenesulfonate (V-71) 1-n-heptyl-4- [N- (4-methoxyphenyl) aminocarbonylaminomethyl] pyridinium -Hexafluorophosphate (V-72) 1-methyl-4- (N, N-dimethylaminocarbonyl-N'-methylaminomethyl) pyridinium-tetrafluoroborate

  As content of the onium compound in the said photosensitive composition, 0.1-30 mass% is preferable, 0.5-20 mass% is more preferable, 0.5-15 mass% is especially preferable.

-Hydrogen donor compound-
The photopolymerization initiating compound preferably contains a hydrogen donor compound.
The hydrogen donor compound is particularly a compound that is excited by active energy rays and can donate hydrogen (electrons) by interacting with the acridine derivative and the neutral radical generator. There is no limitation and can be appropriately selected according to the purpose. For example, α-dialkylaminoacetophenone compound, tertiary amino hydrocarbon compound, dialkylaniline compound, aminobenzoic acid ester compound, mercapto compound, phosphorus compound, containing active hydrogen Examples thereof include hydrocarbon compounds, oxime ether compounds, borate compounds, and the like.

  Examples of the α-dialkylaminoacetophenone compound include compounds represented by the following general formulas (VI-1) to (VI-4).

However, in the general formulas (VI-1) to (VI-4), Ar ¹ represents an aromatic group represented by the following formulas (iv) to (vii).

X ¹ is any one of groups represented by the following formula (viii), —NR ¹³¹ —, —N (R ¹³¹ ) —R ¹³² —N (R ¹³¹ ) —.
Y ¹ represents any one of an alkylene group having 1 to 6 carbon atoms, a xylylene group, a cyclohexylene group, and a direct bond, and Y ² represents a xylylene group, an alkenediyl group having 4 to 8 carbon atoms, and 6 to 6 carbon atoms. It represents any one of 10 alkanediene diyl groups, dipentene diyl groups, and dihydroxyrylene groups.
U represents any of —O—, —S—, and —N (R ¹³⁷ ) —, and V represents —O—, —S—, —N (R ¹³⁷ ) —, —CO—, —CH _2. —, —CH ₂ CH ₂ —, an alkylidene group having 2 to 6 carbon atoms, and a direct bond, W is a straight chain, branched chain, alkylene group having 1 to 7 carbon atoms, and carbon An alkylidene group having 2 to 6 atoms is represented.
R ¹²¹ is bonded to the group represented by the following formula (ix), the group represented by the following formula (x), the group represented by the following formula (xi), and R ¹³² , and the following formula (xii) or One of the groups represented by (xiii) is represented.

However, p represents 0 or 1 in the formula (ix), and q represents 0 to 3 in the formula (xi). Ar ² is a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 12 carbon atoms, —N (R ¹¹ ) ₂ , an alkyne group having 1 to 12 carbon atoms, —COO (having 1 to 18 carbon atoms) Alkyl) group, —CO (OCH ₂ CH ₂ ) nOCH ₃ (n represents 1 to 20), or —OCO (C 1-4) alkyl substituted with an alkyl group. group, -COO alkyl group having 1 to 18 carbon _{atoms, -CO (OCH 2 CH 2)} nOCH 3 ( representative of n is 1 to 20.), or --OCO (1 to 4 carbon atoms) substituted by an alkyl group alkoxy group having 1 to 12 carbon atoms, which is substituted by -COO group (alkyl of 1 to 18 carbon _{atoms), -CO (OCH 2 CH 2} ) nOCH 3 (n represents 1-20.) Alkoxy having 1 to 4 carbon atoms _{Group, - (OCH 2 CH 2)} nOH, - (OCH 2 CH 2) nOCH 3 (. N is representing 1-20), an alkylthio group having 1 to 8 carbon atoms, a phenoxy group, -COO (number of carbon atoms 1-18 alkyl) _group, a _{-CO (OCH 2 CH 2) nOCH} 3 (n is 1 to 20.), a phenyl group, or a phenyl group substituted by a benzyl group, a naphthyl group, a furyl group, a thienyl group And any of pyridyl groups.
In the formula (xiii), m represents 1 or 2.

R ¹²² is a carbon atom substituted by the group described in R ¹²¹ , a cycloalkyl group having 5 or 6 carbon atoms, a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, a halogen atom or a phenyl group. It represents any one of an alkyl group having 1 to 12 and a phenyl group substituted by a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
Wherein ^{R 123} is substituted hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, -CN, an alkyl group or -COO alkyl group having 1 to 4 carbon atoms And an alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a phenylalkyl group having 7 to 9 carbon atoms.
R ¹²⁴ represents an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a —CN (alkyl having 1 to 4 carbon atoms) group, or —COO (1 to 1 carbon atom). Alkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a phenylalkyl group having 7 to 9 carbon atoms. A phenyl group substituted by a phenyl group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a —COO (alkyl having 1 to 4 carbon atoms) group, R ¹²² and Bonded alkylene group having 1 to 7 carbon atoms, phenylalkylene group having 7 to 10 carbon atoms, o-xylylene group, 2-butenylene group, oxa group having 2 to 3 carbon atoms, and 2 to 2 carbon atoms Representing the azaalkylene group.
R ¹²³ and R ¹²⁴ may be bonded via —O—, —S—, —CO— or —N (R ¹³⁷ ) —, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, And an alkylene group having 3 to 7 carbon atoms which can be substituted by a -COO (alkyl having 1 to 4 carbon atoms) group.
R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , and R ¹²⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group. , Benzyl group, benzoyl group, —OR ¹³⁸ , —SR ¹³⁹ , —SO—R ¹³⁹ , —SO ₂ R ¹³⁹ , N (R ¹⁴⁰ ) (R ¹⁴¹ ), —NH—SO ₂ —R ¹⁴² , and the following formula ( xiv).

However, in the above formula (xiv), Z is ^{-O -, - S -, -} N (R 131), - N (R 131) -R 132 -N (R 131), and any said formula (viii) Represents In the formula (xiv), when R ¹²¹ represents an allyl group and R ¹²² represents a methyl group, R ¹²⁵ does not represent —OCH ₃ , R ¹²¹ represents a benzyl group, and R ¹²² represents When representing a methyl group and a benzyl group, R ¹²⁵ does not represent —OCH ₃ , —SCH ₃ , or —SO—CH ₃ .

R ¹³⁰ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkanoyl group having 2 to 8 carbon atoms.
R ¹³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, And a phenyl group.
R ¹³² represents a linear alkylene group having 2 to 16 carbon atoms, which may be bonded via one or more —O—, —S—, or —N (R ¹¹ ) —, and a branched chain. Represents an alkylene group having 2 to 16 carbon atoms.
R ¹³³ represents any one of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a phenyl group.
R ¹³⁴ , R ¹³⁵ and R ¹³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ¹³⁴ and R ¹³⁵ are bonded to form an alkylene group having 3 to 7 carbon atoms. To express.
R ¹³⁷ is a hydrogen atom, one or more —O—, an alkenyl group having 3 to 5 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, —CH ₂ CH ₂ It may be via a CN (alkyl having 1 to 4 carbon atoms) group, a —CH ₂ CH ₂ COO (alkyl having 1 to 4 carbon atoms) group, an alkanoyl group having 2 to 8 carbon atoms, and a benzoyl group. An alkyl group having 1 to 12 carbon atoms is represented.
R ¹³⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, —CN, —OH, an alkoxy group having 1 to 4 carbon atoms, an alkenoxy group having 3 to 6 carbon atoms, or —OCH ₂ CH ₂ CN. , substituted by -OCH ₂ CH ₂ COO group (alkyl of 1 to 4 carbon atoms) group (alkyl of 1 to 4 carbon atoms), -COOH (alkyl of 1 to 4 carbon atoms) group or -COO alkyl group having 1 to 6 carbon _{atoms, - (CH 2 CH 2 O} ) nH (. representing the n is 2 to 20), alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, A cyclohexyl group, a hydroxycyclohexyl group, a phenyl group, a halogen atom, a phenyl group substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and 7 to 9 carbon atoms Phenylalkyl group or -Si (alkyl of 1 to 8 carbon atoms) _{gamma (phenyl) 3-gamma} group (gamma represents. 1-3) representative of.
R ¹³⁹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, —SH (alkyl having 1 to 4 carbon atoms), —OH (number of carbon atoms). 1-4 alkyl), - CN (alkyl of 1 to 4 carbon atoms), - COO (alkyl) group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon _atoms, -OCH 2 _CH 2 CN Or an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogon atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom substituted by a —OCH ₂ CH ₂ COO (alkyl having 1 to 4 carbon atoms) group A phenyl group substituted by an alkoxy group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms is represented.
R ¹⁴⁰ and R ¹⁴¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or the number of carbon atoms. An alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a phenyl group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to 1 carbon atom 4 of the phenyl group substituted by an alkoxy group, or represents alkanoyl group or benzoyl group having a carbon number of 2 to ^{3, R 140} and ^{R 141} are bonded to -O -, - S- or -N ^{(R 137} )-, Or an alkyle having 2 to 8 carbon atoms which can be substituted by a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or a -COO (alkyl having 1 to 4 carbon atoms) group. Represents a group.
R ¹⁴² is an alkyl group having 1 to 18 carbon atoms, a hydrogen atom, a halogen atom, a phenyl group substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or a naphthyl group. Represents.

Examples of the compound represented by the general formula (VI-1) include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2- (dimethylamino) -2-ethyl. -1- (4-morpholinophenyl) -4-penten-1-one, 2- (dimethylamino) -2-methyl-1- (4-morpholinophenyl) -4-penten-1-one, 2-benzyl- 2- (dimethylamino) -1- (4-morpholinophenyl) propan-1-one, 4-morpholino-4- (4-morpholinobenzyl) hepta-1,6-diene, 2-ethyl-2-morpholino-1 -(4-morpholinophenyl) -4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- [4- (dimethylamino) -phenyl] -butan-1-one, 4-dimethylamino -4- (4-Dimethyl Aminobenzoyl) -hepta-1,6-diene, 4- (dimethylamino) -4- (4-morpholinobenzoyl) -hepta-1,6-diene, 2- (dimethylamino) -2- (4-dimethylamino) Phenyl) -2-ethyl-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -2-butan-1-one, 2-benzyl-2- ( Dimethylamino) -1- [4- (dimethylamino) phenyl] -4-penten-1-one, 2-benzyl-1- [4- (dimethylamino) phenyl] -2- (dimethylamino) 3-phenyl- Provan-1-one, 2-ethyl-1- [4- (methylthio) phenyl] -2-morpholino-4-penten-1-one, 4- [4- (methylthio) benzoyl] -4-morpholinohepta-1 , 6-Diene, 4- (dimethyl Mino) -4- (4-methoxybenzoyl) hepta-1,6-diene, 4- (4-methoxybenzoyl) -4-morpholino-hepta-1,6-diene, 1- (4-methoxyphenyl) -2 -Morpholino-2-phenyl-4-penten-1-one, 2-ethyl-1- (4-methoxyphenyl) -2-morpholino-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- [4- (methylthio) phenyl] -butan-1-one, 2- (dimethylamino) -2-ethyl-1- [4- (methylthio) phenyl] -4-penten-1-one, 2- Benzyl-2- (dimethylamino) -1- [4- (methylthio) phenyl] -4-penten-1-one, 4- (dimethylamino-4- [4- (methylthio) benzoyl] -1,6-heptadiene 2- (Dimethylamino) -3- (4- Fluorophenyl) -2-methyl-1- [4- (methylthio) -phenyl] -propan-1-one, 3- (4-chlorophenyl) -2- (dimethylamino) -2-methyl-1- [4- (Methylthio) phenyl] -propan-1-one, 3- (2-chlorophenyl) -2- (dimethylamino) -2-methyl-1- [4- (methylthio) -phenyl] -propan-1-one, 3 -(4-Bromophenyl) -2- (dimethylamino) -2-methyl-1- [4- (methylthio) phenyl] -propan-1-one, 2-ethyl-4-methyl-1- [4- ( Methylthio) phenyl] -2-morpholino-4-penten-1-one, 2-ethyl-1- [4- (methylthio) phenyl] -2-morpholino-4-hexen-1-one, 2-benzyl-1- [4- (Methylthio) phenyl] -2-morpholine -4-penten-1-one, 2-allyl-1- [4- (methylthio) phenyl] -2-morpholino-hexane-1-one, 2- (dimethylamino) -1- [4- (methylthio) phenyl ] -2-Methyl-3- (4-methyl-phenyl) -propan-1-one, 2- (dimethylamino) -1,3-bis [4- (methylthio) phenyl] -2-propan-1-one 2- (dimethylamino) -1- [4- (methylthio) phenyl] -2-methyl-3- (4-methoxy-phenyl) -propan-1-one, 1- [4- (methylthio) phenyl]- 2-methyl-2-morpholino-4-penten-1-one, 2- (dimethylamino) -1- [4- (methylthio) phenyl] -2-methyl-4-penten-1-one, 1- [4 -(Methylthio) phenyl] -2-morpholino-2-phenyl-4 -Penten-1-one, 2- (dimethylamino) -1- [4- (methylthio) phenyl] -2-phenyl-4-penten-1-one, 2- (dimethylamino) -1- [4- ( Methylthio) phenyl] -2,3-diphenylpropan-1-one, 2-methyl-2-morpholino-1- (4-morpholinophenyl) -4-penten-1-one, 2-benzyl-2-morpholino-1 -(4-morpholinophenyl) -4-penten-1-one, 2-ethyl-2-morpholino-1- (4-morpholinophenyl) -4-penten-1-one, 1- [4- (dimethylamino) Phenyl] -2-methyl-2-morpholino-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -3-phenyl-propan-1-one, 4 -[4- (dimethylamino) -Benzoyl] -4-morpholino-hepta-1,6-diene, 2- (dimethylamino) -1- [4- (dimethylamino) phenyl] -2-methyl-4-penten-1-one, 2-benzyl 2- (dimethylamino) -1- (4-morpholinophenyl) -4-penten-1-one, 1- [4- (dimethylamino) phenyl] -2-ethyl-4-methyl-2-morpholino-4 -Penten-1-one, 1- [4- (dimethylamino) phenyl] -2-ethyl-2-morpholino-hexen-1-one, 2-ethyl-2-morpholino-1- (4-morpholinophenyl)- 4-hexen-1-one 2-ethyl-4-methyl-2-morpholino-1- (4-morpholinophenyl) -4-penten-1-one, 1- [4- (bis- (2-methoxyethyl) Amino) phenyl] -2-methyl- -Morpholino-4-penten-1-one, 1- [4- (dibutylamino) phenyl] -2-methyl-2-morpholino-4-penten-1-one, 2-methyl-1- [4- (4 -Methyl-piperazin-1-yl) phenyl] -2-morpholino-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (4-methoxyphenyl) -butan-1-one, 1- [4- (Diethylamino) phenyl] -2-methyl-2-morpholino-4-penten-1-one, 2-methyl-2-morpholino-1- [4- (pyrrolidin-1-yl) phenyl]- 4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (4-piperidinophenyl) -butan-1-one, 2-ethyl-2- (dimethylamino) -1- ( 4-piperazinophenyl) -4-penten-1-o 2-benzyl-1- [4- (diethylamino) phenyl] -2-ethyl-butan-1-one, 1- [4- (diethylamino) phenyl] -2-ethyl-4-penten-1-one, 2 -Benzyl-2- (dimethylamino) -1- [4- (2-hydroxyethylthiophenyl) -butan-1-one, 2-ethyl-1- [4- (2-hydroxyethylthio) phenyl] -2 -Morpholino-4-penten-1-one, 1- [4- (diallylamino) phenyl] -2-methyl-2-morpholino-4-penten-1-one, 3- (4-benzoylphenyl) -2- (Dimethylamino) -2-methyl-1- [4- (methylthio) phenyl] -propan-1-one, 2- (dimethylamino) -3- (3,4-dimethoxyphenyl) -2-methyl-1- Phenyl-propan-1-one, 2- ( Dimethylamino) -3- (3,4-dimethoxyphenyl) -2-methyl-1- [4- (methylthio) phenyl] propan-1-one, 3- (4-benzoylphenyl) -2- (dimethylamino) 2-methyl-1-phenyl-propan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-fluorophenyl) butan-1-one, 4- (dimethylamino) -4- ( 4-fluorobenzoyl) -hepta-1,6-diene, 2-ethyl-2-morpholino-1- [4- (4-methylphenylsulfonyl) phenyl] -4-penten-1-one, 2- (dimethylamino ) -2-ethyl-1- [4- (methylsulfonyl) phenyl] -4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- [4- (methylphenylsulfonyl) phenyl] butane -1-one, 2- 2- (dimethylamino) -1- [4- (methylsulfonyl) phenyl] butan-1-one, 1- (4-fluorophenyl) -2-methyl-2-morpholino-4-penten-1-one 4- (4-fluorobenzoyl) -4-morpholinohepta-1,6-diene, 2-benzyl-2- (dimethylamino) -1- (4-fluorophenyl) -4-penten-1-one, -Benzyl-2- (dimethylamino) -1- (4-fluorophenyl) -3-phenylpropan-1-one, 2- (dimethylamino) -2-ethyl-1- (4-fluorophenyl) -4- Penten-1-one, 2-benzyl-1- (4-fluorophenyl) -2-morpholino-4-penten-1-one, 2-ethyl-1- (4-fluorophenyl) -2-morpholino-4- Penten-1-one, 2-be Zir-2- (dimethylamino) -1- (4-fluorophenyl) propan-1-one, 2- (dimethylamino) -1- (4-fluorophenyl) -2-methyl-4-penten-1-one 2-benzyl-2- (dimethylamino) -1- (4-hydroxyphenyl) butan-1-one, 2-benzyl-1- [4- (ethoxycarbonylmethoxy) phenyl] -2- (dimethylamino) butane -1-one, 2-benzyl-2- (dimethylamino) -1- [4- (2-hydroxyethyloxy) phenyl] butan-1-one, 2-benzyl-1- (4-chlorophenyl) -2- (Dimethylamino) butan-1-one, 2-benzyl-1- (4-bromophenyl) -2- (dimethylamino) butan-1-one, 1- (4-bromophenyl) -2-ethyl-2- Morpholino-4-penten-1-o 2-ethyl-1- (4-methoxyphenyl) -2-morpholino-3-penten-1-one, 2- (dimethylamino) -2-ethyl-1- (4-methoxyphenyl) -4-pentene -1-one, 2-benzyl-1- [4- (dimethylamino) phenyl] -2-morpholino-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- [4- ( Dimethylamino) phenyl] propan-1-one, 2-methyl-2- (morpholino) -1-phenyl-4-penten-1-one, 2-benzyl-2-morpholino-1-phenyl-4-pentene-1 -One, 2- (dimethylamino) -2-methyl-1-phenyl-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1-phenyl-propan-1-one, 4-benzoyl -4- (dimethylamino) -he 1,6-diene, 2-benzyl-2- (dimethylamino) -1,3-diphenyl-propan-1-one, 2-benzyl-2- (dimethylamino) -1-phenyl-4-pentene- 1-one, 2- (dimethylamino) -2-ethyl-1-phenyl-4-penten-one, 2-benzyl-2- (dimethylamino) -1-phenyl-butan-1-one, 1,2- Diphenyl-2-morpholino-4-penten-1-one, 3- (4-chlorophenyl) -2- (dimethylamino) -2-methyl-1-phenylpropan-one, 3- (4-bromophenyl) -2 -(Dimethylamino) -2-methyl-1-phenyl-propan-1-one,
3- (2-Chlorophenyl) -2- (dimethylamino) -2-methyl-1-phenyl-propan-1-one, 3- (3,4-dimethoxyphenyl) -2- (dimethylamino) -2-methyl -1-phenyl-propan-1-one, 2- (dimethylamino) -2-methyl-3- (4-methylphenyl) -1-phenyl-propan-1-one, 2- (dimethylamino) -2- Methyl-3- [4- (methylthio) phenyl] -1-phenyl-propan-1-one, 2- (dimethylamino) -3- (4-fluorophenyl) -2-methyl-1-phenyl-propane-1 -One, 2- (dimethylamino) -3- (4-methoxy-phenyl) -2-methyl-1-phenyl-propan-1-one, 2-ethyl-1- (4-fluorophenyl) -4-methyl -2-morpholino-4-penten-1-o 2-ethyl-1- (4-fluorophenyl) -5-methyl-2-morpholino-4-penten-1-one, 2- (benzylmethylamino) -2-ethyl-1- (4-morpholinophenyl) -4-penten-1-one, 2- (allylmethylamino) -2-ethyl-1- (4-morpholinophenyl) -4-penten-1-one, 2-benzyl-2- (benzylmethylamino)- 1- (4-morpholinophenyl) -4-butan-1-one, 2-benzyl-2- (butylmethylamino) -1- (4-morpholinophenyl) -4-butan-1-one, 2- (butyl Methylamino) -1- (4-morpholinophenyl) -4-penten-1-one, 1- (4-acetylaminophenyl) -2-benzyl-2-dimethylamino-butan-1-one, 2-benzyl- 2-Dimethylamino-1- (4 Morpholinophenyl) pentan-1-one, 2-allyl-2-dimethylamino-1- (4-morpholinophenyl) pentan-1-one, 2-morpholino-1- [4- (2-methoxyethyloxy) phenyl] 2-methyl-4-pentenone, 4-morpholino-4- [4- (2-hydroxyethylthio) benzoyl] -5-methyl-1-hexene, 1- (4-bromophenyl) -2-morpholino 2-methyl-4-penten-1-one, 4- (4-bromobenzoyl) -4-morpholino-5-methyl-1-hexene, 1- (4- [2-hydroxyethylthio] phenyl) -2 -Methyl-2-morpholino-4-penten-1-one, 1- (4- [2- (allyloxy) -ethoxy] phenyl) -2-ethyl-2-morpholino-4-penten-1-one, 1- (4- [2 -(Allyloxy) -ethoxy] phenyl) -2-methyl-2-morpholino-4-penten-1-one, 1- (4- [2- (methoxy) -ethoxy] phenyl) -2-methyl-2-morpholino -4-penten-1-one, 2-benzyl-2-dimethylamino-1- [4- (2-methoxyethylamino) phenyl] -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-Methylaminophenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- [4- (N-acetylmethylamino) phenyl] -butan-1-one, 2-benzyl-2- Diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-diethylamino-2-ethyl-1- (4-morpholinophenyl) -4-penten-1-one, 2-benzyl-2- (dimethyla ) -1- (3,5-dimethyl-4-methoxy-phenyl) -butan-1-one, 2-benzyl-1- (2,4-dichlorophenyl) -2- (dimethylamino) -butane-1- ON, 2- (dimethylamino) -2-ethyl-1- (3,4-dichlorophenyl) -4-penten-1-one, 2-benzyl-1- (3,4-dichlorophenyl) -2- (dimethylamino) ) -Butan-1-one, 1- (3-chloro-4-morpholinophenyl) -2- (dimethylamino) -butan-1-one, 2-benzyl-1- (3-chloro-4-morpholinophenyl) 2- (dimethylamino) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylamino-3-ethylphenyl) -butan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-dimethylamino-2-me Tilphenyl) -butan-1-one, 9-butyl-3,6-di (2-benzyl-2-dimethylaminobutyryl) carbazole, 9-butyl-3,6-di (2-methyl-2-) Morpholino-4-penten-1-one-1-yl) -carbazol, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one-trifluoroacetate, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one-p-toluenesulfonate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one-camphor-sulfonate, 4- (dimethylamino) -4- [4- (phenoxy) -benzoyl] -hepta-1,6-diene, 2-benzyl-2- (dimethylamino) -1 -(4-Isopropyl Xylphenyl) -4-penten-1-one, 1- (4-butyloxyphenyl) -2-ethyl-2-morpholino-4-penten-1-one, 1- (4-allyloxyphenyl) -2-benzyl 2- (dimethylamino) -butan-1-one, 2-methyl-2-morpholino-1- [4- (trimethylsilyloxy) phenyl] -4-penten-1-one, 2-benzyl-2- (dimethyl) Amino) -1- [4-((1,1,2-trimethylpropyldimethyl) silyloxy) phenyl] butan-2-one, 2-ethyl-1- [4- (ethylthio) phenyl] -2-morpholino-4 -Penten-1-one, 2-benzyl-1- [4- (butylthio) phenyl] -2- (dimethylamino) -3-phenyl-propan-1-one, 1- [4- (isopropylthio) phenyl] -2-methyl Ru-2-morpholino-4-penten-1-one, 1- [4- (allylthio) phenyl] -2-ethyl-2-morpholino-4-penten-1-one, 1- [4- (benzylthio) phenyl ] -2-Benzyl-2- (dimethylamino) -propan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-mercaptophenyl) -butan-1-one, 2-benzyl-1 -[4- (cyclohexylthio) phenyl] -2- (dimethylamino) -3-phenyl-propan-1-one, 2-ethyl-1- [4- (4-methylphenylthio) phenyl] -2-morpholino -4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- [4- (octylthio) phenyl] -butan-1-one, 2-benzyl-1- [4- (chlorophenylthio) Phenyl] -2- (dimethyl) Amino) -4-penten-1-one, 2-methyl-1- [4- (2-methoxycarbonylethylthio) phenyl] -2-morpholino-4-penten-1-one, 1- [4- (butyl Sulfinyl) phenyl] -2- (dimethylamino) -2-ethyl-4-penten-1-one, 1- [4- (benzenesulfonyl) -phenyl] -2-benzyl-2- (dimethylamino) butane-1 -One, 2-benzyl-2- (dimethylamino) -1- [4- (methylsulfinyl) phenyl] -butan-1-one, 2-ethyl-1- [4- (4-methylphenylsulfonyl) phenyl] 2-morpholino-4-penten-1-one, 1- (3,4-dimethoxyphenyl) -2-ethyl-2-morpholino-4-penten-1-one, 2-benzyl-1- (3,4 -Dimethoxyphenyl) -2 -(Dimethylamino) butan-1-one, 4- (3,4-dimethoxybenzoyl) -4- (dimethylamino) hepta-1,6-diene, 1- (1,3-benzodioxol-5-yl ) -2-Benzyl-2- (dimethylamino) -butan-1-one, 1- (1,3-benzodioxol-5-yl) -2-methyl-2-morpholino-4-penten-1-one 2-benzyl-2- (dimethylamino) -1- (3,4,5-trimethoxyphenyl) butan-1-one, 1- (dibenzofuran-3-yl) -2-ethyl-2-morpholino-4 -Penten-1-one, 1- (4-benzoylphenyl) -2-benzyl-2- (dimethylamino) propan-1-one, 2- [2-benzyl-2- (dimethylamino) butanoyl] -fluorenone, 2- (2-Methyl-2-morpholino-4- Pentenoyl) -xanthone, 2- [2-allyl-2- (dimethylamino) -4-pentenoyl] -acridanone, 2- [2-benzyl-2- (dimethylamino) butanoyl] -dibenzosuberone, 1- (N -Butylcarbazol-3-yl) -2-ethyl-2-morpholino-4-penten-1-one, 2-benzyl-1- (N-butylcarbazol-3-yl) -2- (dimethylamino) -Butan-1-one, 2-allyl-2- (dimethylamino) -1- (N-methylphenothiazin-2-yl) -4-penten-1-one, 2-benzyl-1- (N-butyl- Phenoxazin-2-yl) -2-morpholino-propan-1-one, 2-benzyl-2- (dimethylamino) -1- (xanthen-2-yl) -butan-1-one, 1- (chroman- 6-yl) -2-ethyl 2-morpholino-4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (N-methylindoline-5-yl) -propan-1-one, 1- (N-butylindoline- 5-yl) -2-ethyl-2-morpholino-4-penten-1-one,
1- (5,10-dibutyl-5,10-dihydrophenazin-6-yl) -2- (dimethylamino) -4-penten-1-one, 2-benzyl-1- (1,4-dimethyl-1 , 2,3,4-Tetrahydroquinoxalin-6-yl) -2- (dimethylamino) butan-1-one, 1- (1,4-dibutyl-1,2,3,4-tetrahydroquinoxalin-6-yl ) -2-Ethyl-2-morpholino-4-penten-1-one, 2-benzyl-1- (2,3-dihydro-2,3-dimethylbenzothiazol-5-yl) -2- ( Dimethylamino) butan-1-one, 1- (2,3-dihydrobenzofuran-5-yl) -2-methyl-2-morpholino-4-penten-1-one, 2-benzyl-1- (2,3 -Dihydrobenzofuran-5-yl) -2- (dimethylamino) -buta 2-one, 1- (4-aminophenyl) -2-benzyl-2- (dimethylamino) -butan-2-one, 1- [4- (butylamino) phenyl] -2-methyl-2-morpholino -4-penten-1-one, 2-butyl-2- (dimethylamino) -1- [4- (isopropylamino) -phenyl] -butan-1-one, 2-ethyl-1- (4-methoxyphenyl) ) -2-piperidino-4-penten-1-one, 2-methyl-2- (N-methylpiperazino) -1- [4- (N-methylpiperazino) phenyl] -4-penten-1-one, 2-benzyl 2- [di (2-methoxyethyl) -amino] -1- [4- (thiomethyl) phenyl] -butan-1-one, 2- (dibutylamino) -1- (4-methoxyphenyl) -2- Methyl-4-penten-1-one, 1- [4- (dimethyl) Amino) -phenyl] -2-ethyl-2- (methylphenylamino) -4-penten-1-one, 2-methyl-1- (methoxyphenyl) -2-oxazolidino-4-penten-1-one, 2 -Ethyl-1- (4-morpholinophenyl) -2-piperazino-4-penten-1-one, 2-methyl-2-pipericino-1- (4-piperidinophenyl) -4-penten-1-one 2-ethyl-1- [4- (methylthio) phenyl] -2-piperidino-4-penten-1-one, 2-benzyl-2- (dibutylamino) -1- [4- (methylthio) phenyl]- Butan-1-one, 2- (dibutylamino) -2-methyl-1- [4- (dimethylamino) phenyl] -4-penten-1-one, 2-benzyl-2- (dibutylamino) -1- (4-morpholinophenyl) -butane- -One, 2- (dimethylamino) -1- [4- (dimethylamino) -phenyl] -2-[(1-chlorohexenyl) -methyl] -butan-1-one, 2- (dimethylamino) -2 -(2-Chloropentenyl) -1- (4-morpholinophenyl) -propan-1-one, 2-ethyl-2- (4-morpholinobenzoyl) -N-methyl-1,2,3,6-tetrahydropyridine 2- (dimethylamino) -1- [4- (dimethylamino) phenyl] -2,4,5-trimethyl-4-hexen-1-one, 2- (dimethylamino) -1- [4- (dimethyl Amino) phenyl] -2- (2-pinen-10-yl) -butan-1-one, 2-benzyl-2- (dimethylamino) -1- [4- (2,6-dimethylmorpholin-4-yl) ) Phenyl] -butan-1-one, 2-ethyl-2- (2,6 -Dimethylmorpholin-4-yl) -1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -4-penten-1-one, 1- [4- (dimethylamino) phenyl] -2 -Ethyl-2- (2,6-dimethylmorpholin-4-yl) -4-penten-1-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-methyl- 2-morpholino-4-penten-1-one, 2-ethyl-1- [4- (2-hydroxyethoxy) phenyl] -2-morpholino-4-penten-1-one, 1- [4- (2- Methoxyethyloxy) phenyl] -2-methyl-2-morpholino-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-propyl-4-pentene- 1-one, 2-benzyl-2- (dimethyl) Ruamino) -1- [4- (2-methoxyethylthio) phenyl] -butan-1-one, 2- (dimethylamino) -2-isopropyl-1- (4-morpholinophenyl) -4-pentene-1- ON, 2-benzyl-1- (3,5-dichlorophenyl) -2- (dimethylamino) -butan-1-one, 1- (3,5-dichloro-4-methoxyphenyl) -2-methyl-2- Morpholino-4-penten-1-one, 2- (diallylamino) -2-ethyl-1- (4-morpholinophenyl) -4-penten-1-one, 1- [4- (dimethylamino) phenyl]- 2-methyl-2- (pyrrolidin-1-yl) -4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (4-methylphenyl) butan-1-one, 1- ( 4-dodecylphenyl) -2-ethyl-2-morpholino 4-penten-1-one, 2-methyl-1- (4-methylphenyl) -2-morpholino-4-penten-1-one, 2-ethyl-2-morpholino-1- (4-morpholinophenyl)- 4-penten-1-one dodecylbenzenesulfonate, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one dodecylbenzenesulfonate, 2-dimethylamino- 2- (4-dodecylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- (4-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 2-dimethylamino-2- (4-isopropylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-1- (4-dimethylaminophenyl) -1- (4- Methylbenzyl) butan-1-one, 2-dimethylamino-2- (4-hydroxymethylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- [4- (acetoxyethyl) benzyl)] 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4- [2- (2-methoxyethoxy) ethyloxy] benzyl) -1- (4-morpholino Phenyl) butan-1-one, 2-dimethylamino-2- (4- [2- (2- [2-methoxyethoxy] ethoxycarbonyl) ethyl] benzyl) -1- (4-morpholinophenyl) butane-1- ON, 2- (4- [2-bromoethyl] benzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4- [2-diethylaminoethyl] benzyl) -2- Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-1- (4-dimethylaminophenyl) -2- (4-dodecylbenzyl) butan-1-one, 2-dimethylamino -1- (4-Dimethylaminophenyl) -2- (4-isopropylbenzyl) butan-1-one, 2-dimethylamino-2- (3,4-dimethylbenzyl) -1- (4-morpholinophenyl) butane -1-one, 2-dimethylamino-2- [4- (2- (2-methoxyethoxy) ethoxycarbonyl) benzyl] -1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- (4-butylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane- 1- 2- (dimethylamino) -2- (4-isobutylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2-benzyl-2- (dimethylamino) -1- (4- [3 -Methoxypropylamino] phenyl) -butan-1-one, 1- (4- [N-acetyl-3-methoxypropylamino] phenyl) -2-benzyl-2- (dimethylamino) butan-1-one, 2 -Benzyl-2- (di [2-methoxyethyl] amino) -1- (4-morpholinophenyl) butan-1-one, 2-ethyl-2- (di [2-methoxyethyl] amino) -1- ( 4-morpholinophenyl) -4-penten-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) hexane-1-one, 2-benzyl-2- (dimethylamino)- 1- (4-morpholinophenyl) hept Tan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) octan-1-one, 2-benzyl-2- (dimethylamino) -4,5,5-trimethyl- 1- (4-morpholinophenyl) hexane-1-one, 2- (dimethylamino) -2- (4-methoxybenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- (4-butoxy (Benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4- [2-hydroxyethoxy] benzyl) -1- (4- Morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4- [2-methoxyethoxy] benzyl) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-Isopropylbenzyl)- 1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-dodecylbenzyl) -1- (4-morpholinophenyl) octane-1-one, 2- (dimethylamino) 2- (2-Isopropylbenzyl) -1- (4-morpholinophenyl) pentan-1-one, 2- (dimethylamino) -1- (4- (dimethylamino) phenyl-2- (4- [2- Methoxy] benzyl) heptan-1-one, 2- (butylmethylamino) -2- (4-isopropylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 2- (4-isobutylbenzyl)- 2- (butylmethylamino) -1- (4-morpholinophenyl) pentan-1-one, 2- (4-methylbenzyl) -2- (dioctylamino) -1- (4-morpholinophenyl) hexane-1- ON, 2- (4-butoxy (Benzyl) -2- (butylmethylamino) -1- (4-morpholinophenyl) pentan-1-one, 2- (4-butylbenzyl) -2- (butylmethylamino) -1- (4-morpholinophenyl) Hexane-1-one, and the like.

  Examples of the tertiary amino hydrocarbon compound include a tertiary amine compound represented by the following general formula (VII-1) and an aliphatic amino acid ester compound represented by the following general formula (VII-2). .

However, in the general formula (VII-1), R ⁵¹ and R ⁵² are each independently a hydroxyl- or alkoxy-substituted lower alkyl group, a hydroxyl- or alkoxy-substituted cycloalkyl group, an alkyl- or Represents an alkoxy-substituted phenyl group, a hydroxyl group, and a lower alkoxy group, or R ⁵¹ and R ⁵² represent an alkylene group by cyclic bonding.
R ¹⁵³ represents the group described for R ¹⁵¹ or R ¹⁵² , a hydrogen atom, a saturated or unsaturated acyloxy group, or an alkyl-, alkoxy-, halogen- and / or dialkylamino-substituted benzoyloxy group.
R ¹⁵⁴ and R ¹⁵⁵ each independently represent either a hydroxy-substituted lower alkyl group, a hydroxy-substituted cycloalkyl group, and an alkyl- or alkoxy-substituted phenyl group, or R ⁴ and R ⁵ is cyclically bonded to each other and represents either an alkylene group or an alkyleneoxyalkylene group.
In the general formula (VII-2), X represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a nitro group, an amino group, or a halogen atom. , An acyl group, and a carboxyl group, and n is an integer of 1 to 5. R ¹⁵⁶ and R ¹⁵⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group, or an aralkyl group, and R ¹⁵⁷ represents a hydrogen atom Represents an alkyl, benzyl group having 1 to 4 carbon atoms which may be substituted with an atom, a hydroxy group, a methylthio group, or a —COOR ³ group, and R ¹⁵⁶ and R ¹⁵⁷ are 6-membered together with an N atom and adjacent carbon atoms A ring may be formed.

  Examples of the tertiary amine compound represented by the general formula (VII-1) include 1-dimethylamino-2-phenyl-2-methylpropane, 1-dimethylamino-3-methoxy-2,2-dimethylbroban. 1-dimethylamino-3-acetoxy-2,2-dimethylpropane, 1-diethylamino-3-isopropyloxy-2,2-dimethylbropan, 3-N, N-pentamethylene-2,2-dimethylpropanol -1,1-dimethylamino-3-acryloyloxy-2,2-dimethylbroban, 1-dimethylamino-3-methacryloyloxy-2,2-dimethylpropane, 1-dimethylamino-3-benzoyloxy-2,2 -Dimethylpropane, 1-dimethylamino-3-p-dimethylaminobenzoyl-2,2-dimethylpropane, Etc., and the like. Among these, 3-bis- (2-hydroxyethyl) -amino-2,2-dimethylbropanol-1, 3-bis- (2-hydroxybropyraminoamino-2,2-dimethylbropanol-1 are 3-Dimethylamino-2,2-dimethylbropanol-1 is more preferable.

  The aliphatic amino acid ester compound represented by the general formula (VII-2) is not particularly limited, and examples thereof include N-phenylglycine, N- (p-acetylphenyl) glycine, N- (m-trifluoro). Methylphenyl) glycine, N- (m-acetylphenyl) glycine, N- (p-trifluoromethylphenyl) glycine, N-phenylalanine, N-phenylserine, N-phenylthreonine, N-phenylcysteine, N-phenylproline N-phenylglutamic acid, N-phenylglycine, benzyl ester, and the like. The glycine derivative may be a bipolar ion compound containing an amino cation and a carboxylic acid anion in the structure. Among these, N-phenylglycine is particularly preferable.

  Examples of the dialkylaniline compound include compounds represented by the following general formula (VII-3).

However, in said general formula (VII-3), R ^<159> and R ^<160 > is an alkyl group which has 1-6 carbon atoms, and it is preferable that the said carbon atom is 1-4. n is an integer of 1 to 5, and X ³ is a substituent having a Hammett (σ) (para) constant of −0.9 to 0.7.

  Examples of the compound represented by the general formula (VII-3) include 4-cyano-N, N-dimethylaniline, 4-acetyl-N, N-dimethylaniline, 4-bromo-N, N-dimethylaniline. , Ethyl-4- (N, N-dimethylamino) benzoate, 3-chloro-N, N-dimethylaniline, 4-chloro-N, N-dimethylaniline, 3-ethoxy-N, N-dimethylaniline, 4- Fluoro-N, N-dimethylaniline, 4-methyl-N, N-dimethylaniline, 4-ethoxy-N, N-dimethylaniline, N, N-dimethylthioanisidine, 4-amino-N, N-dimethylaniline 3-hydroxy-N, N-dimethylaniline, N, N, N ′, N′-tetramethyl-1,4-diaminobenzene, 4-acetamido-N, N-dimethyl Diphosphate, and the like.

  Examples of the aminobenzoic acid ester compounds include dimethylaminobenzoic acid ester compounds represented by the following general formula (VII-4), dialkylaminobenzophenones represented by the following general formula (VII-5), and the like. .

In the general formula (VII-4), R ¹⁶¹ is an alkyl group having 1 to 12 carbon atoms, aryl groups having 6 to 14 carbon atoms, a cycloalkyl group having 5 to 40 carbon atoms, And an aralkyl group having 7 to 20 carbon atoms.
Moreover, in said general formula (VII-5), R ^<162> and R ^<163 > represent a C1-C6 alkyl group each independently. X ⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an NR ⁶² R ⁶³ group.

  Examples of the dimethylaminobenzoate compound represented by the general formula (VII-4) include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, n-hexyl p-dimethylaminobenzoate, p -N-heptyl dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, 2-dodecyl p-dimethylaminobenzoate, cyclohexyl p-dimethylaminobenzoate, benzyl p-dimethylaminobenzoate, and the like. Of these, 2-ethylhexyl p-dimethylaminobenzoate is most preferred.

  Examples of the compound represented by the general formula (VII-5) include 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4-di-n-propylaminobenzophenone, 4,4′-bis (dimethylamino). Examples include benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (di-n-propylamino) benzophenone, and the like. Of these, 4,4'-bis (diethylamino) benzophenone is most preferred.

  Examples of the mercapto compound include mercapto compounds represented by the following general formulas (VIII-1a) and (VIII-1b), thioether compounds represented by the following general formula (VIII-2), and the following general formula (VIII- 3), a compound represented by the following general formula (VIII-4), and the like.

R ¹⁶⁴ represents an alkyl group or an aryl group, and R ¹⁶⁵ represents a hydrogen atom or an alkyl group.
As said alkyl group of R ^{< 164>} , R ^<165>, a C1-C4 thing is preferable. In addition, the aryl group represented by R ¹⁶⁴ is preferably a phenyl group, a naphthyl group or the like having 6 to 10 carbon atoms. And those substituted with an alkoxy group such as methoxy group and ethoxy group. R ¹⁶⁴ and R ¹⁶⁵ may be an atomic group necessary for bonding to complete a heterocyclic ring which may have a condensed ring together with a carbon atom or a nitrogen atom. Examples of the condensed ring include a benzene ring.

However, in said general formula (VIII-2), R ^<166> represents either an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkenyl group, R ^<167> and R ^{<168 >} are the same meaning as R ^<166 >, Alternatively, it represents a group having a positive Hammett σ _p value.
In the general formula (VIII-3), R ¹⁶⁹ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, either alkenyl group and ^Y 3 -CS-S- of, ^{Y 3} is, -OR It represents ⁷⁰ or ^{-NR 171 R 172, R 170,} R 171, and R ¹⁷² is an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an alkenyl group, and a substituted alkenyl group, an R ¹⁷¹ R ¹⁷² may form a ring.
In the above (VIII-4), Z represents R ¹⁷⁵ —SO ₂ —, R ¹⁷⁵ —O—SO ₂ —, R ¹⁷⁵ has the same meaning as R ¹⁷⁰ , R ¹⁷¹ and R ¹⁷² , and R ¹⁷³ and R ¹⁷⁴ represents the same meaning as R ¹⁶⁶ , R ¹⁷⁵ , and Z, or represents a hydrogen atom, a group having a positive Hammett σ _p value, —OR ¹⁶⁶ , or —SR ¹⁶⁶ . R ¹⁶⁶ represents any of the aforementioned alkyl group, substituted alkyl group, aryl group, substituted aryl group, and alkenyl group.

  Examples of the compounds represented by the general formulas (VIII-1a) and (VIII-1b) include thioformamide, thioacetamide, N-methylthioformamide, N-methylthioacetamide, N-phenylthiopropionic acid amide, N- Phenylthiocaproic acid amide, No-chloro-phenylthioacetamide, No-chlorophenylthiocaproic acid amide, Np-tolylthiocaproic acid amide, Nm-methoxyphenylthioacetamide, Nm-methyl Toxiphenylthiopropionic acid amide, Np-ethoxyphenylthioacetamide, Np-ethoxyphenylthiopropionic acid amide, No-methoxyphenylthiocaproic acid amide, 2-mercapto-4,5-dihydro-2- Thiazole, 2-mercapto-4-me -4,5-dihydro-2-thiazole, 2-mercapto-5-methyl-4,5-dihydro-2-thiazole, 2-mercapto-4,4-dimethyl-4,5-dihydro-2-thiazole, 2-mercapto-5,5-dimethyl-4,5-dihydro-2-thiazole, 2-mercapto-4,5-dihydro-2-oxazole, 2-mercapto-4-methyl-4,5-dihydro-2- Oxazole, 2-mercapto-4,4-dimethyl-4,5-dihydro-2-oxazole, 1-methyl-2-mercapto-1,3-imidazole, 2-mercapto-4,5-dihydro-1,3- Thiazine, 2-mercapto-6-methyl-4,5-dihydro-1,3-thiazine, 2-mercapto-4,5-dihydro-1,3-oxazine, 2-mercapto-tetra Dro-1-pyridine, 1- [p- (n-hexylaminocarbonyl) phenyl} -2-mercaptoimidazole, 1- (p-tolyl) -2-mercapto-4,5,6,7-tetrahydro-1, 3-benzimidazole, 2-mercapto-5-methylthio-1,3,4-oxadiazole, 2-mercapto-3,4,5,6-tetrahydro-1-azepine, 2-mercapto-1,3-benz Oxazole, 3-mercapto-5-chloro-1,2-benzisoxazole, 2-mercapto-1,3-benzimidazole, 2-mercapto-6-methoxy-1,3-benzimidazole, 1-methyl-2- Mercapto-1,3-benzimidazole, 2-mercapto-6-methyl-1,3-benzimidazole, 2-mercapto-5,6-dimethyl 1,3-benzimidazole, 2-mercapto-6-methoxy-1,3-benzimidazole, 2-mercapto-5-caproylamino-1,3-benzimidazole, 1- (n-propyl) -2 -Mercapto-1,3-benzimidazole, 1-isopropyl-2-mercapto-1,3-benzimidazole, 2-mercapto-6-chloro-1,3-benzimidazole, 1- (n-heptyl) -2- Mercapto-1,3-benzimidazole, 1- (n-hexyl) -2-mercapto-5-chloro-1,3-benzimidazole, 2-mercapto-6-chloro-1,3-benzimidazole, 1- ( n-octyl) -2-mercapto-5-methoxy-1,3-benzimidazole, 1- (n-hexyl) -2-mercapto-5-eth Cycarbonyl-1,3-benzimidazole, 1- (2-methoxyethyl) -2-mercapto-1,3-benzimidazole, 3-mercapto-6-methyl-1,2-benzothiazole, 1-phenyl-2 -Mercapto-1,3-benzimidazole, 1-phenyl-2-mercapto-5-methylsulfonyl-1,3-benzimidazole, 1- (p-sulfonatomethylphenyl) -2-mercapto-1,3-benz Imidazole sodium salt, 3-mercapto-1,2-benzothiazole, 3-mercapto-6-caproylamino-1,2-benzothiazole, 3-mercapto-6-chloro-1,2-benzothiazole, 3- Mercapto-6-methyl-1,2-benzothiazole, 2-mercapto-naphtho [2,1] -1,3-imida 1- (n-butyl) -2-mercapto-naphtho [2,1] -1,3-imidazole, 1- (n-octyl) -2-mercapto-imidazo [4,5-b] pyridine, 1- (n-octyl) -2-mercapto-imidazo [4,5-b] pyrazine, 1- (n-butyl) -2-mercapto-1,3-imidazo [4,5-b] quinoxaline, 1- (N-hexyl) -2-mercapto-6-chloro-1,3-imidazo [4,5-b] quinoxaline, 1,5-diethyl-3-mercapto-1,2,4-triazole, 4- (n -Hexyl) -3-mercapto-1,2,4-triazole, 4-phenyl-3-mercapto-1,2,4-triazole, 4-phenyl-3-mercapto-5-methylthio-1,2,4- Triazole, 1- (n-hexyl) ) -5-mercaptotetrazole, 1- (n-octyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 2- (n-hexyl) -3-mercapto-1,2,4-oxadiazine, 2 -Phenyl-3-mercapto-5-methyl-1,2,4-thiadiazine, 3-phenyl-4-mercapto-6-phenyl-1,2,3,6-tetrahydro-1,3,5-thiadiazine and the like Can be mentioned. Among these, 1-phenyl-2-mercapto-1,3-benzimidazole is preferable.

  Examples of the thioether compound represented by the general formula (VIII-2) include di-n-butyl sulfide, di-n-octyl sulfide, triphenylthiomethane, diphenylthiomethane, phenylmethyl sulfide, and p-methylthiobenzoic acid. Acid, p-methylthiobenzaldehyde, p-methylthiobenzonitrile, 1-phenylthioethylmethyl ketone, 1-phenylthiopropionitrile, 1-chloromethylphenyl sulfide, 1,3,5-trithiane, 2-methyl-4- Examples include methoxyphenyl methyl sulfide, thiochroman, 4-oxothiochroman and the like.

  Examples of the compound represented by the general formula (VIII-3) include O-isobutyl Sn-butyl dithiocarbonate, O-isobutyl S-benzyl dithiocarbonate, n-butyl diethyldithiocarbamate, benzyl diethyldithiocarbamate, N, N, N ′, N′-tetraethylthiuram disulfide, N, N-diethyl-N ′, N′-di-n-butylthiuram disulfide, 1,2,3-tri (diethyldithiocarbamoylthio) propane, etc. Is mentioned.

  Examples of the compound represented by the general formula (VIII-4) include di-n-butylsulfone, ethyl p-tolylsulfone, p-tolylmethylthiomethylsulfone, acetylmethyl p-tolylsulfone, and bis (p-toluene). Sulfonyl) methane, cyanomethyl p-tolylsulfone, n-butyl p-toluenesulfonate, ethyl methanesulfonate, phenyl acetylmethanesulfonate, diphenylmethanedisulfonate, phenylsulfolane 3-sulfolene cyanomethanesulfonate, and the like.

  Examples of the phosphorus compound include a phosphonic acid diester represented by the following general formula (IX-1) and a phosphorous acid triester represented by the following general formula (IX-2).

However, in General Formula (IX-1), R ¹⁷⁶ represents any of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkenyl group, and R ¹⁷⁷ represents the same meaning as R ¹⁷⁶ , Represents a group having a positive Hammett σ _p value.
In the general formula (IX-2), R ¹⁷⁸ represents any of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkenyl group, and R ¹⁷⁹ and R ¹⁸⁰ have the same meaning as R ^178. Or a group having a positive Hammett σ _p value.

  Examples of the phosphonic acid diester represented by the general formula (IX-1) include dimethyl phosphonate, diethyl phosphonate, di (n-butyl) phosphonate, di (2-ethylhexyl) phosphonate, and ethyl methyl phosphonate. Phosphonate diphenyl, phosphonate ethylphenyl, phosphonate di (p-dimethylaminophenyl), phosphonate di (p-cyanophenyl), phosphonate di (p-acetylphenyl), phosphonate di (p-methoxyphenyl) Phosphonate di (p-tolyl), phosphonate di (o-methoxyphenyl), phosphonate di (o-chlorophenyl), phosphonate di (m-bromophenyl), phosphonate (o-chlorophenyl) (p-methoxy) Phenyl), methylphenyl phosphonate, β-naphthylphenyl phosphonate, phosphonic acid Styrene, propylene phosphonic acid di, trimethylene phosphonic acid, phosphonic acid oxydiethylene, and the like.

  Examples of the phosphite triester represented by the general formula (IX-2) include diethyl phosphite, di-n-butyl phosphite, di (2-ethylhexyl) phosphite, ethyl methyl phosphite, Triethyl phosphite, triphenyl phosphite, diphenyl phosphite, tri (p-dimethylaminophenyl) phosphite, tri (p-cyanophenyl) phosphite, di (p-cyanophenyl) phosphite, Tri (p-methoxyphenyl) phosphite, di (p-methoxyphenyl) phosphite, tri (o-chlorophenyl) phosphite, di (o-chlorophenyl) phosphite, tri (m-bromophosphite) Phenyl), phenyldimethyl phosphite, diphenylmethyl phosphite, phenylmethyl phosphite, dimethyl phosphite (α-naphthyl), ethylene methyl phosphite, ethylene phosphite Eniru phosphite orthoformate ethylene phosphite, tri ethylene, and the like.

  Examples of the active hydrogen-containing hydrocarbon compound include a cyclic β-dicarbonyl compound represented by the following general formula (X-1), a leucotriphenylmethane dye represented by the following general formula (X-2), and the like. .

In the general formula (X-1), R ¹⁸¹ represents any of a substituted or unsubstituted alkyl group and aralkyl group,, G is a divalent organic group, hetero during chain groups It may contain atoms and may have a substituent on at least one of carbon and heteroatoms.
In the general formula (X-2), R ¹⁸² represents any one of an alkyl group having 1 to 6 carbon atoms, R ⁸³ represents any one of an alkyl group having 1 to 6 carbon atoms, and an alkoxy group. , X ⁵ represents any of a phenyl group, a p-aminophenyl group, a p-monoalkylaminophenyl group, a p-dialkylaminophenyl group, and a heterocyclic ring.

  Examples of the cyclic β-dicarbonyl compound represented by the general formula (X-1) include 2,4-diethyl-1,3-cyclobutanedione, 2-methyl-1,3-cycloheptanedione, 5- Methyl-2-thiobarbituric acid, 3-ethyltetronic acid, 2,4-dimethyl-3-oxo-5-hydroxy-5-methoxypentenoic acid δ-lactone, 1,3,5-trimethylbarbituric acid, 1,3 -Dimethyl-5-ethylbarbituric acid, 2-methyl-1,3-cyclopentanedione, 5-methylbarbituric acid, 1,5-dimethylbarbituric acid, 2-methyldimedone, 2-methyl-1,3- Indandione, 1,3-dimethyl-5-benzylbarbituric acid. Bis- [5- (1,3-dimethylbarbituryl))-methane, 1,5-diphenyl-3- [2- (phenylthio) ethyl] -2,4-pyrrolidinedione, 1-phenyl-3,5 -Diketo-4-n-butyl-tetrahydropyrazole, and the like.

  Examples of the leucotriphenylmethane dye represented by the general formula (X-2) include tris (4-N, N-diethylamino-o-tolyl) methanetrihydrochloride, bis (4-N, N-diethylamino-). o-tolyl) thienylmethane, bis (4-N, N-diethylamino-o-tolyl) methylenedithiophenenylmethane, bis (4-N, N-diethylamino-o-tolyl) benzylthiophenylmethane, leucomalachite green (CI Basic Green 4), Leuco Crystal Violet (CI Basin Sink Violet 3), Leuco Brilliant Green (CI Basic Green 1), Leuco Victoria Green 3B (CI Basic Green 4) ), Leuco Acid Green GG (CI Acid Green 3), Leucometi Violet (C.I. Basic Violet 1), leuco rosaniline (C.I. Basic Violet 14), and the like.

  Examples of the oxime ether compound include compounds represented by the following general formula (XI).

However, in the general formula (XI), R ¹⁸⁴ and R ¹⁸⁵ may be the same or different and each may have a substituent, a hydrocarbon group containing an unsaturated bond, and a heterocyclic group Represents one of the following.
R ¹⁸⁶ and R ¹⁸⁷ may be the same or different, and may be a hydrogen atom or a hydrocarbon group containing an unsaturated bond which may have a substituent, a heterocyclic group, a hydroxyl group, a substituted oxy group, It represents either a mercapto group or a substituted thio group. R ¹⁸⁸ and R ¹⁸⁹ represent either a hydrogen atom or a hydrocarbon group containing an unsaturated bond which may have a substituent, and a substituted carbonyl group.
R ¹⁸⁸ and R ¹⁸⁹ represent either a hydrogen atom or a hydrocarbon group containing an unsaturated bond which may have a substituent, or a substituted carbonyl group.

The compound represented by the general formula (XI) is not particularly limited, and examples thereof include 2-dimethylamino-2-methyl-1- (4-methoxyphenyl) propan-1-one-O-allyloxime, 2-methyl-1- (4-methylthiophenyl) propan-1-one-O-allyloxime, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-O-benzyloxime, 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-On-butyloxime, 2-methyl-2-morpholino-1- (4-morpholinophenyl) propan-1-one -O-allyloxime, 2-methyl-1- (4-methoxyphenyl) -2-morpholinopropan-1-one-On-dodecyloxime, 2-methyl- -(4-Methylthiophenyl) -2-morpholinopropan-1-one-O-2- (2-methoxyethoxy) ethyloxime, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On-O-4-methoxycarbonylbenzyloxime, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-O-methoxycarbonylmethyloxime, 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropan-1-one-O-ethoxycarbonylmethyloxime, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-O- (4-methoxycarbonyl) butyl Oxime, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-o -O- (2-methoxycarbonyl) ethyloxime, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one-O-3-methoxycarbonyl-2-propenyloxime 2-methyl-1 -(4-methylthiophenyl) -2-morpholinopropan-1-one O-benzyloxycarbonylmethyloxime, and the like.

  Examples of the borate compound include organic boron compounds represented by the following general formula (XII).

However, in the general formula (XII), Ra ¹ , Ra ² , and Ra ³ are each independently any one of an aliphatic group, an aromatic group, a heterocyclic group, and —SiRa ⁵ Ra ⁶ Ra ^7. To express. Ra ⁵ , Ra ⁶ and Ra ⁷ each independently represent an aliphatic group or an aromatic group. Ra ⁴ represents an aliphatic group. Y ⁺ represents a group that forms a cation.

  Examples of the organic boron compound represented by the general formula (XII) include tetra (n-butyl) ammonium-n-butyltriphenylborate, tetraethylammonium diphenylmethylsilyltriphenylborate, and tetramethylammonium diphenylmethylsilyl. Triphenylborate, tetra (n-hexyl) ammonium-n-hexyltriphenylborate, tetra (n-butyl) ammonium-n-butyldi (p-fluorophenyl) phenylborate, tetra (n-butyl) ammonium- n-butyltri (p-fluorophenyl) borate, tetra (n-butyl) ammonium-n-hexyltri (p-chlorophenyl) borate, tetra (n-butyl) ammonium-n-hexyldi (p-chlorophenyl) phenyl Tetra (n-butyl) ammonium di (n-hexyl) di (m-fluorophenyl) borate, tetra (n-butyl) ammonium-n-hexyltri (2-methyl-5-fluorophenyl) borate, tetra (n -Butyl) ammonium methyl dimesityl phenyl borate, and the like.

  Among these hydrogen donor compounds, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -2-butan-1-one, 1-phenyl-2-mercapto-1,3-benz Imidazole, N-phenylglycine, 4,4′-bis (diethylamino) benzophenone, leucocrystal violet, 2-dimethylamino-2-methyl-1- (4-methoxyphenyl) propan-1-one-O-allyloxime, Tetra (n-butyl) ammonium-n-butyltriphenylborate is particularly preferred.

  The amount of the hydrogen donor compound in the photopolymerization initiating compound is preferably 0.02 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1.5 to 10% by mass.

[Photosensitive composition for solder resist]
The solder resist photosensitive composition includes a binder, a polymerizable compound, the photopolymerization initiating compound, a thermal crosslinking agent, a thermosetting accelerator, and preferably the hydrogen donor. Agent, inorganic filler, and other ingredients.

<Binder>
As a binder in the said photosensitive composition for soldering resists, it is preferable that it is swellable with respect to alkaline aqueous solution, for example, and it is more preferable that it is soluble with respect to alkaline aqueous solution. Moreover, it is preferable to have photocrosslinkability.
The alkali-soluble refers to the property that the photosensitive composition for a solder resist containing it is dissolved by an alkaline developer, and specifically, it should be soluble to the extent that the desired development processing is performed. That's fine. The alkaline developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal hydroxides such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydroxyethylamine, triethylamine Or an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide or a mixture thereof with a miscible organic solvent. pH is 8-14 and 0.01-10 mass% aqueous solution of these alkali agents is preferable. Among these alkaline developers, in the printed wiring board industry, 0.2 to 2 mass% sodium carbonate aqueous solution is generally used, and 1 mass% sodium carbonate aqueous solution is the most common.
An example of the development method is as follows. The surface of the copper-clad laminate is prepared by pressure-bonding the photosensitive layer with a laminator while peeling the protective film of the pattern-forming material on the surface of the dried copper-clad laminate. A laminate comprising a photosensitive layer and a support film is prepared. The pressure bonding conditions are a laminate temperature of 70 ° C., a pressure roll temperature of 105 ° C., a pressure roll pressure of 3 kg / cm ^2, and a pressure bonding speed of 1.2 m / min.
The support film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.1 MPa over the entire surface of the photosensitive layer on the copper-clad laminate. If the photosensitive layer on the copper clad laminate is removed after spraying for at least 60 seconds, it will be developed.
Such an alkali-soluble resin can be suitably selected from those showing a solubility of 1% by mass or more in a 1% by mass sodium carbonate aqueous solution at 30 ° C., for example.
The photocrosslinking property refers to a property of changing a linear polymer molecule into a network having a three-dimensional network structure by photochemical reaction. Specifically, free radicals generated by photolysis of a photopolymerization initiator are used. It refers to a polymer that can be networked by polymerization reaction.
Such an alkali-soluble resin can be suitably selected from those showing a solubility of 1% by mass or more in a 1% by mass sodium carbonate aqueous solution at 30 ° C., for example.
The photocrosslinking property refers to a property of changing a linear polymer molecule into a network having a three-dimensional network structure by photochemical reaction. Specifically, free radicals generated by photolysis of a photopolymerization initiator are used. It refers to a polymer that can be networked by polymerization reaction.

The binder (hereinafter also referred to as alkali-soluble photocrosslinkable resin) is a resin soluble in a 1% aqueous sodium carbonate solution (pH = 10) containing an alkali-soluble group and a crosslinkable group involved in photopolymerization in the molecule. It is.
There is no restriction | limiting in particular as said alkali-soluble photocrosslinkable resin, According to the objective, it can select suitably, For example, a vinyl polymer type photocrosslinkable resin, an epoxy resin ester type photocrosslinkable resin, etc. are mentioned.

-Vinyl polymer type photocrosslinkable resin-
The vinyl polymer photocrosslinkable resin is classified into the following types (A-1), (A-2) and (A-3), and is selected from at least one of the types.
Type (A-1): produced by reaction of (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.
Type (A-2): (c) An epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound are subjected to an addition reaction, and (e) a polybasic acid anhydride is converted into a hydroxyl group of the resulting product. Produced by addition reaction.
Type (A-3): produced by addition reaction of (f) a copolymer resin containing an acid anhydride group and (g) a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule. The
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

-Type (A-1)-
The (a) carboxyl group-containing copolymer resin used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-1) is one unsaturated group and at least one carboxyl group in one molecule or It is obtained by copolymerizing a compound having an acid anhydride group and at least one of (meth) acrylic acid ester and styrenes.

  The compound (a) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule having the carboxyl group-containing copolymer resin as a structural unit is (meth) acrylic acid, Include those containing two or more carboxyl groups in the molecule, such as maleic acid and itaconic acid. Also included are maleic acid, itaconic acid monoesters, or monoamides. Moreover, the half ester compound which is a reaction product of a hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride is mentioned. These half ester compounds can be obtained by reacting a hydroxyl group-containing (meth) acrylate with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio.

  Examples of the hydroxyl group-containing acrylate used in the synthesis of the half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane. Examples include di (meth) acrylate, pendaerythritol tri (meth) acrylate, diventaerythritol penta (meth) acrylate, and the like.

Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyl nadrahydrophthalic anhydride, ethyl tetrahydro Examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like. Of these, (meth) acrylic acid is preferred.
These compounds having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester that constitutes the structural unit of the carboxyl group-containing copolymer resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meta ) Acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate , Β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meta ) Acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of the styrenes constituting the structural unit of the carboxyl group-containing copolymer resin (a) include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, Butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methyl Examples include styrene.
The (a) carboxyl group-containing copolymer resin comprises a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, a (meth) acrylic acid ester monomer, and styrene. It is obtained by copolymerization by a usual copolymerization method with at least one of the above classes, for example, a solution polymerization method.
In addition, (a) maleic acid monoester / styrene copolymers, maleic acid monoamide / styrene copolymers, itaconic acid monoester / styrene copolymers, and itacon included in the carboxyl group-containing copolymer resin. In the case of acid monoamide / styrene copolymers, obtain by polymer reaction of maleic anhydride / styrene copolymers or itaconic anhydride / styrene copolymers with alcohols or primary or secondary amines, respectively. Can do.

Examples of the alcohols used for the polymer reaction with the maleic anhydride include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, hexanol, and cyclohexanol. Preferable examples include methoxyethanol, ethoxyethanol, methoxypropanol, and ethoxypropanol.
Examples of the primary amines include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, and 6-phenyl-1-hexylamine. , Α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2- Chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- (3-Chlorophenyl) ethyl Amine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, isopropylamine, n -Propylamine, n-butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, phenylamine, 1-naphth Tylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-iso Propoxypropylamine and the like are preferred.
Further, examples of the secondary amines preferably include dimethylamine, diethylamine, methylethylamine, methylpropylamine, diethylamine, ethylpropylamine, dipropylamine, dibutylamine, N, N-methylbenzylamine and the like. Can do.

-(B) Epoxy group-containing unsaturated compound-
As the (b) epoxy group-containing unsaturated compound used in the production of the vinyl polymer type photocrosslinkable resin of the type (A-1), one radical polymerizable unsaturated group and epoxy group per molecule Examples of the compound include those represented by the following general formulas (1-1) to (1-14).

However, in the general formula _{(1-1) ~ (1-14),} R 14 is a hydrogen atom or a methyl _{group, R 15} is an alkylene group having 1 to 10 carbon _{atoms, R 16} is a hydrocarbon group having 1 to 10 carbon atoms , P represents 0 or an integer of 1-10.
These (b) epoxy group-containing unsaturated compounds may be used alone or in admixture of two or more. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

-Type (A-2)-
The epoxy group-containing copolymer resin (c) used in the production of the vinyl polymer type photocrosslinkable resin of the type (A-2) is a non-reactive (meth) acrylic with an epoxy group-containing monomer and other epoxy groups. It can be obtained by copolymerization with esters and / or styrenes.
As the epoxy group-containing monomer, the compounds described above in the description of the vinyl polymer type photocrosslinkable resin of type (A-1) are preferably used.
At least one of (meth) acrylic acid esters and styrenes that are non-reactive with epoxy groups is a carboxyl group, an alcoholic hydroxyl group, or phenol among the above-mentioned photocrosslinkable resins of type (A-1). Those which do not contain a functional hydroxyl group, an amino group or the like are preferably used.
As a production method, it is obtained by copolymerizing an epoxy group-containing monomer, a non-reactive (meth) acrylic acid ester and styrene with a conventional method such as a solution polymerization method.
Here, the molar ratio of the epoxy group-containing monomer and the (meth) acrylic ester non-reactive with other epoxy groups and at least one of styrenes is preferably 60:40 to 20:80. If the amount of the epoxy group-containing monomer is too small and the molar ratio is larger than 20:80, the amount of addition of the next unsaturated carboxylic acid and polybasic acid anhydride to the copolymer is reduced. If the molar ratio is less than 60:40, the softening point tends to be too low.
Further, the carboxyl group-containing unsaturated compound (d) is one unsaturated group and at least one carboxyl group or acid per molecule in the description of the vinyl polymer type photocrosslinkable resin of type (A-1). As the compound having an anhydride group, the aforementioned compounds can be preferably used.
Further, as the polybasic acid anhydride (e), maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic acid Saturated or unsaturated aliphatic, alicyclic or aromatic compounds having one acid anhydride group in the molecule, such as anhydride, 4-ethyltetrahydrophthalic anhydride and phthalic anhydride are preferred. Among these, tetrahydrophthalic anhydride is particularly preferable.
The reaction of the epoxy group-containing copolymer, the carboxyl group-containing unsaturated compound and the subsequent polybasic acid anhydride is preferably carried out as follows. After addition reaction of 0.8 to 1.2 mol of unsaturated carboxylic acid per one epoxy group equivalent of the copolymer to the epoxy group-containing monomer copolymer, Polybasic acid anhydride is subjected to addition reaction.

-Type (A-3)-
The acid anhydride group-containing resin (f) used for the production of the vinyl polymer type photocrosslinkable resin of type (A-3) is a copolymer of maleic anhydride and styrene or itaconic anhydride and styrene. Obtained by copolymerization.
As the styrene as the copolymer component, those already described in the description of the photocrosslinkable resin of the type (A-1) are preferably used. The copolymer composition ratio of maleic anhydride or itaconic anhydride and styrenes is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70. When it is 90:10 or more, the development resistance of the cured portion is inferior, and when it is 10:90 or less, the developability is inferior.
A copolymer having a mass average molecular weight of about 1,000 to 5,000 obtained by copolymerizing styrene at a ratio of 1 mol to 3 mol with respect to 1 mol of maleic anhydride is preferable. For example, ARCO Chemical Company Examples thereof include SMA ranges 1000, 2000, and 3000.

  Examples of the compound (g) having one hydroxyl group and at least one (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pendaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol mono (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) ) Acid phosphate, glycerol di (meth) acrylate.

The ring-opening addition reaction of the acid anhydride copolymer and a monomer having one hydroxyl group and at least one (meth) acryloyl group in the molecule is performed in an organic solvent containing no active hydrogen. It can be manufactured by the method. Preferred solvents are ethyl acetate, methoxypropyl acetate, methyl ethyl ketone and the like. In this case, the molar ratio of hydroxyl group in the monomer / acid anhydride group in the copolymer is preferably 0.8 to 1.2.
The above ring-opening addition reaction is usually carried out at 50 to 200 ° C., but is preferably about 80 to 150 ° C. in order to prevent formation of diester and gelation. As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, and pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. On the other hand, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine and the like can be added and used in order to prevent the formation of a polymer during the reaction.

As described above, the vinyl polymer photocrosslinkable resin comprising at least one of the types (A-1), (A-2) and (A-3) obtained has an acid value of 50 to 250 mgKOH. / G is required.
The acid value is more preferably from 70 to 200 mgKOH / g, particularly preferably from 90 to 180 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed area with a developing solution that is a weak alkaline aqueous solution. There are harmful effects. The vinyl polymer photocrosslinkable polymer (A) preferably has a mass average molecular weight in the range of 5,000 to 200,000. The mass average molecular weight is more preferably 10,000 to 100,000, and particularly preferably 30,000 to 80,000. When the mass average molecular weight is less than 5,000, the dryness to touch is remarkably inferior and the peelability from the support is inferior. On the other hand, a mass average molecular weight exceeding 200,000 is not preferable because problems such as removability of unexposed portions and storage stability due to an alkaline developer are caused.
The solid content of the alkali-soluble photocrosslinkable resin in the total solid content of the photosensitive solder resist layer is preferably 15 to 70% by mass. If it is less than 15% by mass, the toughness of the cured film is inferior, and if it exceeds 70% by mass, the balance of performance deteriorates such as a decrease in reliability.
In particular, one mixture from the types (A-1) to (A-3) and one mixture from the epoxy resin ester-type photocrosslinkable oligomer described later are preferable because they can provide balanced performance. In this case, the mixing ratio is 10/90 to 90/10 by mass. 20/80 to 80/20 are more preferable, and 30/70 to 70/30 are particularly preferable.

-Epoxy resin ester type photocrosslinkable resin-
The epoxy resin ester-type photocrosslinkable resin is not particularly limited and may be appropriately selected depending on the purpose. For example, (h) an epoxy resin and (i) one unsaturated group in one molecule It produces | generates by further reacting (j) polybasic acid anhydride with the esterification reaction product with the compound which has at least 1 carboxyl group or acid anhydride group.
Examples of the epoxy resin (h) include YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd .; N-665, N-680, N-695 manufactured by Dainippon Ink & Chemicals, Inc .; Nippon Kayaku Co., Ltd. EOCN-102, EOCN-104 manufactured by Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN-299 and other cresol novolac type epoxy resins, and Toto Kasei K.K. -602; DEN-431, DEN-438, DEN-439 manufactured by Dow Chemical Japan Co., Ltd .; EPN-1138, EPN-1235, EPN-1299 manufactured by Ciba Specialty Chemicals Co., Ltd .; Phenol novolac type epoxy resins such as N-730 and N-770 manufactured by the same company may be mentioned. In addition, a part of the novolac type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetra Epoxy resins such as phenylethane type epoxy resins, alicyclic epoxy resins, salicylaldehyde type epoxy resins and the like can also be used advantageously.

Next, the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule is described for the vinyl polymer type photocrosslinkable resin of the type (A-1). Of these, the aforementioned compounds can be preferably used.
Similarly, the polybasic acid anhydride (j) may use the above-mentioned compounds as the component (e) in the description of the vinyl polymer type photocrosslinkable resin of the type (A-2).

--Method for producing epoxy resin ester type photocrosslinkable resin--
There is no restriction | limiting in particular as a manufacturing method of the said epoxy resin ester type photocrosslinkable resin, According to the objective, it can select suitably, For example, the epoxy resin (h) in the case of manufacture, and 1 piece in 1 molecule In the reaction of the unsaturated group with the compound (i) having at least one carboxyl group or acid anhydride group, one unsaturated group per molecule for one equivalent of the epoxy group of the epoxy resin (h) And the compound (i) having at least one carboxyl group or acid anhydride group are preferably reacted at a ratio of 0.8 to 1.05 equivalent, more preferably 0.9 to 1.0 equivalent.
The epoxy resin (h) and the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule are dissolved and reacted in an organic solvent. For example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl Glycol ethers such as ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, fats such as octane and decane Hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha.

Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chlorite, benzyltrimethylammonium chlorite, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the epoxy resin and the vinyl group-containing monocarboxylic acid (b).
Further, it is preferable to use a polymerization inhibitor for preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the amount used is 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount is preferably 0.01 to 1 part by mass. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  The epoxy resin ester-type photocrosslinkable resin is obtained by reacting the reaction product thus obtained with a polybasic acid anhydride (j). The reaction temperature between the reaction product and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

The acid value of the epoxy resin ester type photocrosslinkable resin is adjusted by reacting 0.1 to 1.0 equivalent of polybasic acid anhydride (j) with respect to 1 equivalent of hydroxyl group in the reaction product. it can. The acid value of the epoxy resin ester type photocrosslinkable resin is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric characteristics of the cured film tend to be lowered.
The epoxy resin ester type photocrosslinkable resin preferably has a mass average molecular weight of 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,500. When it is 500 or less, the adhesiveness is too high, and it is difficult to peel off the protective film, and when it exceeds 5,000, it becomes difficult to produce the resin.

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in publications such as JP 50-6034 and JP 51-37193; JP 48-64183, JP 49-4319 Polyester acrylates described in various publications such as JP, JP 30-30490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. It is done. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-75 mass% is preferable and, as for solid content in solid content of the said photosensitive composition for soldering resists of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur. If it exceeds 75% by mass, the adhesiveness of the photosensitive solder resist layer becomes strong. This is not preferable.

<Thermal crosslinking agent>
There is no restriction | limiting in particular as said heat-crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned suitably.
The epoxy resin and the polyfunctional oxetane compound are not particularly limited and may be appropriately selected depending on the intended purpose. For example, curing of the photosensitive solder resist layer formed using the photosensitive composition for solder resist. An epoxy resin compound having at least two oxirane groups in one molecule, an oxetane compound having at least two oxetanyl groups in one molecule, etc. within a range that does not adversely affect developability and the like in order to improve the film strength later Can be used.

  There is no restriction | limiting in particular as said epoxy resin, According to the objective, it can select suitably, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000; Japan Epoxy Resin Co., Ltd." etc.) or mixtures thereof, isocyania Heterocyclic epoxy resins having a nurate skeleton ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type Epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A Borac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032” , EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), epoxy resins having a dicyclopentadiene skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.”), glycidyl Examples thereof include a methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  The polyfunctional oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3 -Oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3 -Methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers thereof or In addition to polyfunctional oxetanes such as copolymers, oxetane groups and Novo And ether compounds with hydroxyl groups such as poly (p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes, etc., and oxetane A copolymer of an unsaturated monomer having a ring and an alkyl (meth) acrylate is also included.

  There is no restriction | limiting in particular as solid content in solid content of the said photosensitive composition solution for solder resists of the said epoxy resin or a polyfunctional oxetane compound, According to the objective, it can select suitably, for example, 2 50 mass% is preferable and 3-30 mass% is more preferable. If the solid content is less than 2% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance and electroless plating resistance may be reduced. If it exceeds mass%, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

-Other thermal crosslinking agents-
The other thermal crosslinking agent can be added separately from the epoxy resin and the polyfunctional oxetane compound. The thermal crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. For example, a polyisocyanate compound described in JP-A-5-9407 can be used. As the polyisocyanate compound, It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups.
Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanate; An adduct of the polyfunctional alcohol with an alkylene oxide adduct and the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Over preparative and cyclic trimer of such derivatives, and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive composition for solder resist or the photosensitive layer (hereinafter also referred to as photosensitive solder resist film), the polyisocyanate and its derivatives are blocked on the isocyanate groups. You may use the compound obtained by making an agent react.
There is no restriction | limiting in particular as said isocyanate group blocking agent, According to the objective, it can select suitably, For example, isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam; phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. Phenols such as amylphenol, p-octylphenol and p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethylated methylol melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

<Thermosetting accelerator>
The thermosetting accelerator has a function of accelerating the thermosetting of the epoxy resin compound or the polyfunctional oxetane compound, and is preferably added to the photosensitive resin.
The thermosetting accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy. Amine compounds such as -N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole and 2-methyl Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole Any imidazole derivatives bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts, boron trifluoride-amine complex, organic hydrazide cumulative, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) , Benzo Aromatic acid anhydrides such as phenonetetracarboxylic anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac Etc. can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the polyfunctional oxetane compound is a curing catalyst, or any compound capable of promoting the reaction of the carboxyl group with these, and any compound capable of promoting thermal curing other than the above. May be used.
The solid content in the solid content of the photosensitive composition solution for a solder resist of the epoxy resin, the polyfunctional oxetane compound, and a compound capable of accelerating thermal curing between these and a carboxylic acid is usually 0.01 to 20% by mass.

<Inorganic filler>
The inorganic filler can improve the surface hardness of the permanent pattern, can keep the coefficient of linear expansion low, and can keep the dielectric constant and dielectric loss tangent of the cured layer itself low. It can be suitably used for the photosensitive composition for use.
The inorganic filler is not particularly limited and can be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor-phase process silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

The average particle size of the inorganic filler is preferably less than 3 μm, more preferably 0.1 to 2 μm. If the average particle size is 3 μm or more, resolution may be deteriorated due to light scattering.
5-75 mass% is preferable, as for the addition amount of the said inorganic filler, 8-70 mass% is more preferable, and 10-65 mass% is especially preferable. When the addition amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently reduced. When the addition amount exceeds 90% by mass, when a cured film is formed on the surface of the photosensitive solder resist layer, The film quality of the cured film becomes fragile, and when a wiring is formed using a permanent pattern, the function as a protective film for the wiring may be impaired.

Further, organic fine particles can be added as necessary. Suitable organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle size of 0.1 to ² μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  Since the inorganic filler contains particles having an average particle diameter of 0.1 to 2 μm, even if the permanent pattern is thinned to a thickness of 5 to 20 μm along with the thinning of the printed wiring board, The inorganic filler particles do not cross-link the front and back surfaces of the permanent pattern, and as a result, no ion migration occurs even in the high acceleration test (HAST), and a permanent pattern excellent in heat resistance and moisture resistance can be obtained. .

<Colorant>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, dyes, such as a coloring pigment selected suitably from well-known dyes, can be used.

-Color pigment-
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more.

  The solid content in the solid content of the photosensitive composition solution for the solder resist of the color pigment may be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive solder resist layer during permanent pattern formation. Although it varies depending on the type of the color pigment, it is generally preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass.

<Other ingredients>
The other component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents, adhesion promoters, thermal polymerization inhibitors, plasticizers, and other additives. Adhesion promoters and other auxiliaries (eg, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer) Or other agents) may be used in combination. By appropriately containing these components, it is possible to adjust the properties such as stability, photographic properties, film physical properties, etc. of the target photosensitive composition for solder resist or photosensitive solder resist film.

-Solvent-
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

-Adhesion promoter-
The adhesion promoter has a function of improving adhesion between layers, adhesion between a photosensitive solder resist layer and a substrate, and electrolytic corrosion.
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine. Commercially available triazine compounds include Shikoku Kasei Kogyo Co., Ltd. shown in the following structural formulas (E) to (G); 2MZ-AZINE (structural formula (E)), 2E4MZ-AZINE (structural formula (F)), CllZ -AZINE (Structural Formula (G)) and the like can be given.

  These compounds increase the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more. The content of the adhesion promoter is preferably 0.1 to 40% by mass and more preferably 0.1 to 20% by mass with respect to the solid content of the photosensitive composition for solder resist.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor is preferably added to prevent thermal polymerization or temporal polymerization of the polymerizable compound and improve storage stability.
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound Such as chelates with Al and the like.

  As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

-Other additives-
The other additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents such as benton, montmorillonite, aerosol, amide wax, silicone-based, fluorine-based, and polymer-based. Additives such as antifoaming agents and leveling agents can be used.

[Photosensitive composition for etching resist]
The photosensitive composition for an etching resist includes at least a binder, a polymerizable compound, and the photopolymerization initiation system compound, and includes other components that are appropriately selected according to the purpose.

<Binder>
The binder in the photosensitive composition for an etching resist is preferably, for example, swellable with an alkaline liquid, and more preferably soluble in an alkaline liquid.
As the binder exhibiting swellability or solubility with respect to the alkaline liquid, for example, those having an acidic group are preferably mentioned.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. A vinyl copolymer having a carboxyl group is preferable from the viewpoint of solubility, suitability for synthesis, ease of adjustment of film properties, and the like. From the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The other copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters. , Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes (eg styrene, styrene derivatives, etc.), (meth) acrylonitrile, complex substituted with vinyl groups Cyclic groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate ( 2-Acryllo Ciethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), vinyl monomers having a functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group) and the like. Among these, the styrenes (styrene and styrene derivatives) are preferable in that a permanent pattern such as a wiring pattern can be formed with high definition and the tent property can be improved.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

However, in the above structural formula (1) ~ (3), R 1 represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

There is no restriction | limiting in particular as content rate of the polymeric compound which has a carboxyl group in the said vinyl copolymer, Although it can select suitably according to the objective, For example, 5-50 mol% is preferable, 10-40 mol % Is more preferable, and 15 to 35 mol% is particularly preferable.
If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

There is no restriction | limiting in particular as molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, 2,000-300,000 are preferable as a mass mean molecular weight, 4,000-150 1,000 is more preferable.
When the mass average molecular weight is less than 2,000, the strength of the film tends to be insufficient and stable production may be difficult, and when it exceeds 300,000, developability may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  In addition, as the binder, a resin soluble in an alkaline liquid described in Japanese Patent No. 2873890 can be used.

There is no restriction | limiting in particular in content of the said binder in the said photosensitive composition, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, 20-80 mass% is more preferable, 40 ˜80 mass% is particularly preferred.
When the content is less than 10% by mass, alkali developability and adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. Stability and strength of the cured film (tent film) may be reduced. The content may be the total content of the binder and the polymer binder used in combination as necessary.

When the binder is a substance having a glass transition temperature (Tg), the glass transition temperature is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive composition is used. 80 degreeC or more is preferable, 100 degreeC or more is more preferable, and 120 degreeC or more is preferable from the viewpoint of at least any one of suppression of tack and edge fusion of the formed photosensitive layer, and improvement of the peelability of the support in the pattern forming material. Particularly preferred.
When the glass transition temperature is less than 80 ° C., the tackiness or edge fusion of the photosensitive layer formed using the photosensitive composition may increase, or the peelability of the support may deteriorate.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 mgKOH / g, more preferably 90 to 200 mgKOH / g, and 100 to 180 mgKOH / g. Particularly preferred.
If the acid value is less than 70 mgKOH / g, developability may be insufficient or resolution may be inferior, and a wiring pattern or the like may not be obtained with high definition. If the acid value exceeds 250 mgKOH / g, At least one of the developer resistance and adhesion may deteriorate, and the wiring pattern or the like may not be obtained with high definition.

<Polymerizable compound>
The polymerizable compound in the photosensitive composition for an etching resist is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monomer or oligomer having at least one of a urethane group and an aryl group may be used. Preferably mentioned. Moreover, it is preferable that these have 2 or more types of polymeric groups.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

--Monomer having urethane group--
The monomer having a urethane group is not particularly limited as long as it has a urethane group, and can be appropriately selected depending on the purpose. For example, JP-B-48-41708, JP-A-51-37193, JP-B-5 -50737, Japanese Patent Publication No. 7-7208, Japanese Patent Application Laid-Open No. 2001-154346, Japanese Patent Application Laid-Open No. 2001-356476, and the like. For example, a polyisocyanate compound having two or more isocyanate groups in the molecule And an adduct of a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, A diisocyanate such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; a polyaddition product of the diisocyanate with a bifunctional alcohol (in this case, both ends are isocyanate groups); a burette or isocyanurate of the diisocyanate; Trimer; the diisocyanate or diisocyanates and trimethylolpropane, pe Taeritoritoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

  In addition, examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Is mentioned. Among these, the compound represented by the following structural formula (13) or the structural formula (14) is preferable, and it is particularly preferable that at least the compound represented by the structural formula (14) is included from the viewpoint of tent properties. Moreover, these compounds may be used individually by 1 type, and may use 2 or more types together.

In the structural formulas (13) and (14), R ^{201 to} R ²⁰³ each represent a hydrogen atom or a methyl group. X ₁ to X ₃ represents an alkylene oxide, may be alone or in combination of two or more thereof.

  Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

  In the structural formulas (13) and (14), m1 to m3 represent an integer of 1 to 60, preferably 2 to 30, and more preferably 4 to 15.

In the structural formulas (13) and (14), Y ¹ and Y ² represent a divalent organic group having 2 to 30 carbon atoms, for example, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group. (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, Preferred examples include a sulfonyl group (—SO ₂ —) or a combination thereof, and among these, an alkylene group, an arylene group, or a combination thereof is preferable.

  The alkylene group may have a branched structure or a cyclic structure, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, trimethyl hexene. Preferable examples include a xylene group, a cyclohexylene group, a heptylene group, an octylene group, a 2-ethylhexylene group, a nonylene group, a decylene group, a dodecylene group, an octadecylene group, or any of the groups shown below.

  The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and the groups shown below.

  Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine). Atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, , Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

  In the structural formulas (13) and (14), n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of feedability of raw materials for synthesizing a polymerizable monomer.

  In the structural formulas (13) and (14), Z represents an n-valent (trivalent to hexavalent) linking group, and examples thereof include any of the groups shown below.

However, _{X 4} represents an alkylene oxide. m4 represents an integer of 1 to 20. n represents an integer of 3 to 6. A represents an n-valent (trivalent to hexavalent) organic group.

  Examples of A include an n-valent aliphatic group, an n-valent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, and an imino group. Are preferably a combination of a substituted imino group in which the hydrogen atom is substituted with a monovalent hydrocarbon group or a sulfonyl group, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group or arylene A group in which a group and an oxygen atom are combined is more preferable, and an n-valent aliphatic group, and a group in which an n-valent aliphatic group is combined with an alkylene group and an oxygen atom are particularly preferable.

  As the number of carbon atoms of A, for example, an integer of 1 to 100 is preferable, an integer of 1 to 50 is more preferable, and an integer of 3 to 30 is particularly preferable.

The n-valent aliphatic group may have a branched structure or a cyclic structure.
As a carbon atom number of the said aliphatic group, the integer of 1-30 is preferable, for example, the integer of 1-20 is more preferable, and the integer of 3-10 is especially preferable.
The number of carbon atoms of the aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and particularly preferably an integer of 6 to 30.

  The n-valent aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group ( Examples thereof include an acetoxy group, a butyryloxy group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), and the like.

The alkylene group may have a branched structure or a cyclic structure.
As a carbon atom number of the said alkylene group, the integer of 1-18 is preferable, for example, and the integer of 1-10 is more preferable.

The arylene group may be further substituted with a hydrocarbon group.
As the number of carbon atoms of the arylene group, an integer of 6 to 18 is preferable, and an integer of 6 to 10 is more preferable.

  As a carbon atom number of the monovalent hydrocarbon group of the said substituted imino group, the integer of 1-18 is preferable and the integer of 1-10 is more preferable.

  Below, the preferable example of said A is as follows.

  Examples of the compounds represented by the structural formulas (13) and (14) include compounds represented by the following structural formulas (15) to (34).

  However, in said structural formula (15)-(34), n, n1, n2 and m mean 1-60, l means 1-20, R represents a hydrogen atom or a methyl group. .

--Monomer having an aryl group--
The monomer having an aryl group is not particularly limited as long as it has an aryl group, and can be appropriately selected depending on the purpose. For example, a polyhydric alcohol compound having a aryl group, a polyvalent amine compound, and a polyvalent Examples thereof include esters or amides of at least one of amino alcohol compounds and unsaturated carboxylic acid.

  Examples of the polyhydric alcohol compound, polyamine compound or polyhydric amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1, 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetra Methyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4- Diol, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylene-di-2-naphth 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α -(1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like can be mentioned. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable monomer Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, etc.), styrene Compounds such as divinylbenzene, p-allylstyrene, p-isopropenestyrene, and the like. Among these, a compound represented by the following structural formula (35) is preferable.

In the structural formula (35), R ²⁰⁴ and R ²⁰⁵ each represents a hydrogen atom or an alkyl group.

In the structural formula (35), X ₅ and X ₆ represent an alkylene oxide group, which may be used alone or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, a group in which these are combined (which may be combined in any of random and block), Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a group combining these is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.

  In the structural formula (35), m5 and m6 are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15.

In the structural formula (35), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula (35), Ar ¹ and Ar ² represent an aryl group which may have a substituent, and examples thereof include phenylene and naphthylene. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

  Specific examples of the monomer having an aryl group include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth)). (Acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group (For example, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-((Meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecae) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (e.g. 2,2-bis (2) having 2 to 20 ethoxy groups substituted with one phenolic OH group 4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxy) Pentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) pheny ) Propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or both the polyethylene oxide skeleton and the polypropylene oxide skeleton in the same molecule as the polyether moiety Compounds (for example, compounds described in WO01 / 98832 etc., or commercially available, Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000), bisphenol skeleton and urethane group Examples thereof include a polymerizable compound. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

  Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product. Examples thereof include compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.).

-Other polymerizable monomers-
In the pattern forming method of the present invention, a polymerizable monomer other than the monomer containing the urethane group and the monomer having an aryl group may be used in combination as long as the characteristics as the pattern forming material are not deteriorated.

  Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate A di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, a compound described in WO01 / 98832), at least one of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate Examples include relate and xylenol di (meth) acrylate.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1, Preference is given to 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate added with ethylene oxide, and the like.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonate ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester of the isocrotonic acid and the aliphatic polyhydric alcohol compound (isocrotonate ester) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and diethylenetriamine bis (meth) acrylamide.

  In addition to the above, as the polymerizable monomer, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compound obtained by adding α, β-unsaturated carboxylic acid to glycidyl group-containing compound such as hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, Polyester acrylate and polyester (meth) acrylate as described in JP-B-6183, JP-B-49-43191 and JP-B-52-30490. Rate oligomers, epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) and (meth) acrylic acid and other polyfunctional acrylates and methacrylates such as epoxy acrylates, Journal of Japan Adhesion Association Vol. 20, No. 7, 300-308 Photocurable monomers and oligomers and allyl esters described in page (1984) (eg diallyl phthalate, diallyl adipate, malonic acid) Allyl, diallylamide (eg, diallylacetamide), cationically polymerizable divinyl ethers (eg, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol) Divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol di) Glycidyl ether, diethylene glycol diglycidyl ether, dipropylene group Recall diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.), oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene, etc.), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β- And compounds having two or more different ethylenically unsaturated double bonds, such as methacryloxyethyl) acrylamide and allyl methacrylate.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

  These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

If necessary, the polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.
Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529 pamphlet, Japanese Patent No. 2548016, etc. Is mentioned.

The content of the polymerizable compound in the photosensitive composition is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass.
When the content is less than 5% by mass, the strength of the tent film may be reduced. When the content exceeds 90% by mass, edge fusion during storage of the pattern forming material (a bleed-out failure from the end of the roll) May get worse.
Moreover, 5-100 mass% is preferable, as for content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 20-100 mass% is more preferable, and 40-100 mass% is especially preferable.

<Other ingredients>
Examples of other components in the photosensitive composition for etching resist include known thermal polymerization inhibitors, surfactants, plasticizers, color formers, colorants, and the like, and further adhesion promoters to the substrate surface and Other auxiliaries (for example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc. ) May be used in combination.
In addition, by appropriately containing these components, properties such as stability, photographic properties, print-out properties, and film properties of the target photosensitive layer (the pattern forming material) can be adjusted.
These components may be the same as those contained in the above-mentioned photosensitive composition for solder resist, and by appropriately containing these, properties such as the stability, photographic properties, film physical properties, etc. of the intended photosensitive layer can be obtained. Can be adjusted.

-Plasticizer-
The plasticizer may be added to control film physical properties (flexibility) of the photosensitive layer made of the photosensitive composition.
Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, and the like. Phthalic acid esters: Triethylene glycol diacetate, tetraethylene glycol diacetate, dimethylglycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters of tricresyl phosphate, triphenyl phosphate, etc. Acid esters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl Aliphatic dibasic acid esters such as sepacate, dioctyl azelate, dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,5-diepoxycyclohexane-1,2-dicarboxylic acid Examples include glycols such as dioctyl acid, polyethylene glycol, and polypropylene glycol.

  The content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive composition.

-Color former-
The color former may be added to give a visible image (printing function) to the photosensitive layer after exposure.
Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4- Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-di Aminotriarylmethanes such as propylaminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethyl Aminothioxanthenes such as mino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9- Amino-9,10-dihydroacridine such as phenylacridine, 3,6-bis (benzylamino) -9,10-dividro-9-methylacridine; aminophenoxazine such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylamino) Aminophenylmethanes such as phenyl) anilinomethane; 4-amino-4 ′ Aminohydrocinnamic acids such as dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound which does not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane, but can be oxidized to a coloring compound; Id dyes; U.S. Pat. Nos. 3,042,515 and 3,042 Organic amines that can be oxidized to a colored form as described in No. 517 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole), and among these, triarylmethane compounds such as leuco crystal violet are preferable.

Furthermore, it is generally known that the color former is combined with a halogen compound for the purpose of coloring the leuco body.
Examples of the halogen compound include halogenated hydrocarbons (for example, carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, Diphenylmethyl bromide, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4- Chlorophenyl) ethane); halogenated alcohol compounds (eg, 2,2,2-trichloroethanol, Bromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) Di (2-bromoethyl) ether, 1,2- Chloroethyl ethyl ether, etc.); halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β Halogenated amide compounds (for example, chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2- Trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); a compound having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitro) Phenyl tribromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), e.g., 2,4-bis (trichloromethyl) 6- phenyltriazole and the like. As the organic halogen compound, a halogen compound having two or more halogen atoms bonded to the same carbon atom is preferable, and a halogen compound having three halogen atoms per carbon atom is more preferable. The said organic halogen compound may be used individually by 1 type, and may use 2 or more types together. Among these, tribromomethylphenyl sulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole are preferable.

  The content of the color former is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass with respect to all components of the photosensitive composition. . Moreover, 0.001-5 mass% is preferable with respect to all the components of the said photosensitive composition, and, as for content of the said halogen compound, 0.005-1 mass% is more preferable.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known pigment such as red, green, blue, yellow, purple, magenta, cyan, black, Specifically, Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolite Yellow GT ( CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Yellow) Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH ( Pigment Red 11), Fastel Pink B Spula (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (C CI pigment black 1) and carbon black.

  Examples of the colorant suitable for producing a color filter include C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 83, C.I. I. Pigment violet 23, and those described in JP-A-2002-162752 (0138) to (0141). There is no restriction | limiting in particular as an average particle diameter of the said coloring agent, Although it can select suitably according to the objective, For example, 5 micrometers or less are preferable and 1 micrometer or less is more preferable. Moreover, when producing a color filter, as said average particle diameter, 0.5 micrometer or less is preferable.

-Dye-
In the photosensitive composition, a dye can be used for the purpose of improving handleability or imparting storage stability.
Examples of the dye include brilliant green (for example, sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymolphthalein. , Methyl violet 2B, quinaldine red, rose bengal, metanil-yellow, thymol sulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltylocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzo Purpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuxin, oil blue # 603 (Orien Chemical Co., Ltd.), Rhodamine B, Rhodamine 6G, etc. Victoria Pure Blue BOH can be cited, among these cationic dyes (e.g., Malachite Green oxalate, malachite green sulfates) are preferable. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, for example, a residue such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, toluenesulfonic acid ( Anion) and the like.

  As content of the said dye, 0.001-10 mass% is preferable with respect to all the components of the said photosensitive composition, 0.01-5 mass% is more preferable, 0.1-2 mass% is especially preferable. .

-Adhesion promoter-
The photosensitive composition improves the adhesion of a photosensitive layer formed using the photosensitive composition (adhesion with other layers when used as the pattern forming material, or adhesion with a substrate). Therefore, a known so-called adhesion promoter can be used for each layer.

  Preferable examples of the adhesion promoter include adhesion promoters described in JP-A Nos. 5-11439, 5-341532, and 6-43638. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  As content of the said adhesion promoter, 0.001 mass%-20 mass% are preferable with respect to all the components of the said photosensitive composition, 0.01-10 mass% is more preferable, 0.1 mass%- 5% by mass is particularly preferred.

  The photosensitive composition is, for example, J.P. It may contain organic sulfur compounds, peroxides, redox compounds, azo or diazo compounds, photoreducible dyes, organic halogen compounds, etc. as described in Chapter 5 of “Light Sensitive Systems” Good.

  Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Is mentioned.

  Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide.

  The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides.

  Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diazonium such as 4-aminodiphenylamine.

  Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

-Surfactant-
A known surfactant can be added to the photosensitive composition in order to improve the surface unevenness generated when the pattern forming material of the present invention is produced.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As for content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition for pattern formation materials.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

(Pattern forming material)
The pattern forming material has at least a support and a photosensitive layer made of the photosensitive composition of the present invention on the support, and is laminated with other appropriately selected layers such as a cushion layer according to the purpose. Do it.
As the photosensitive composition, either a photosensitive composition for etching resist or a photosensitive composition for solder resist is included.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

The material of the support is preferably made of a synthetic resin and transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester , Poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, Various plastic films such as polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

  There is no restriction | limiting in particular as a shape of the said support body, It can select suitably according to the objective, For example, it winds up on a cylindrical winding core, and is wound by long shape and roll-shaped and stored. Is preferred. There is no restriction | limiting in particular as length of the said elongate pattern formation material, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. The roll-shaped pattern forming material may be slit into a sheet shape. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

<Photosensitive layer>
The photosensitive layer is formed from the photosensitive composition. There is no restriction | limiting in particular as a location provided in the said pattern formation material of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer may be a single layer or a plurality of layers.

<Other layers>
The other layers in the pattern forming material are not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, and a light absorption layer. You may have layers, such as a layer and a surface protective layer. These layers may be used alone or in combination of two or more. Moreover, you may have a protective film on the said photosensitive layer.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 80 ° C. or lower.
As the thermoplastic resin having a softening point of 80 ° C. or lower, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less, which are soluble in an alkaline solution. In addition, even in an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance so that a substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  In addition, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the pattern forming material is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. With such an interlayer adhesive strength, only the support is peeled off from the laminate, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. be able to. Further, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the laminate, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl Examples include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. A copolymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesion of the pattern forming material is not particularly limited and can be appropriately selected depending on the purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. By setting such an interlayer adhesive strength, the support and the cushion layer are peeled from the laminate, and the photosensitive layer is exposed, and then the photosensitive layer can be developed using an alkaline developer. Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer can be peeled from the laminate, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

There is no restriction | limiting in particular as an ethylene copolymerization ratio in the copolymer which uses the said ethylene as an essential copolymerization component, Although it can select suitably according to the objective, For example, 60-90 mass% is preferable, 60- 80 mass% is more preferable, and 65-80 mass% is especially preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are very easily peeled off, including the cushion layer. It may be difficult to manufacture the pattern forming material.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
If the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Such a problem may occur.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed usually with polyvinyl alcohol as a main component, and is preferably a film having a thickness of about 0.5 to 5 μm.

-Protective film-
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said pattern formation material of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed. Sometimes.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.

[Method for producing pattern forming material]
The pattern forming material can be manufactured, for example, as follows.
First, a material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution for a pattern forming material.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive composition solution is applied onto the substrate or the support and dried to form a photosensitive layer, whereby a pattern forming material can be produced.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

(Photosensitive laminate)
The said photosensitive laminated body laminates | stacks the photosensitive layer which consists of the photosensitive composition of this invention on the said base | substrate, and the other layer suitably selected according to the objective.
The photosensitive composition includes a photosensitive composition for etching resist and a photosensitive composition for solder resist.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed or a transfer target to which at least the photosensitive layer of the pattern forming material of the present invention is transferred, and is not particularly limited, and is appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a substrate for producing a known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, and a metal plate.

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as a first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as a second aspect, at least the pattern forming material of the present invention. Examples of the method include transferring and laminating the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said pattern formation material is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said application | coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said pattern formation material.

In the method for producing a photosensitive laminate according to the second aspect, the pattern forming material of the present invention is laminated on the surface of the substrate while at least one of heating and pressing. In addition, when the said pattern formation material has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular as said heating temperature and pressurization, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular as said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, a laminator (For example, Taisei Laminator company make, VP-II) etc. are mentioned suitably.

(Pattern forming apparatus and pattern forming method)
The pattern forming apparatus of the present invention includes the photosensitive laminate of the present invention, and has at least light irradiation means and light modulation means.

The pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said pattern formation method of this invention.

[Exposure process]
The said exposure process is a process of exposing with respect to the said photosensitive layer in the photosensitive laminated body of this invention. Examples of the photosensitive layer in the photosensitive laminate of the present invention include a photosensitive layer formed from the photosensitive composition of the present invention and a photosensitive layer transferred from the pattern forming material.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation means for irradiating light, and the light irradiation means for irradiating based on the pattern information to be formed. Examples thereof include light modulation means for modulating light.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. For example, the photosensitive layer is arranged in a two-dimensional array of light irradiation means and n pieces (where n is a natural number of 2 or more) that receives and emits light from the light irradiation means. An exposure head comprising a light modulation means capable of controlling the drawing portion in accordance with pattern information, the column direction of the drawing portion relative to the scanning direction of the exposure head Using an exposure head arranged so as to form a predetermined set inclination angle θ, the exposure head is subjected to N-fold exposure (where N is (Natural number of 2 or more) Designation of a grapheme part and control of the pixel part for the exposure head so that only the picturee part designated by the use picture element part designation means is involved in exposure by the picture element part control means It is preferable that the exposure head is moved relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms. Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Further, in the following description, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

<Pattern forming device>
An example of a pattern forming apparatus according to the pattern forming method of the present invention will be described with reference to the drawings.
As the pattern forming apparatus, a so-called flatbed type exposure apparatus is used. As shown in FIG. 1, a sheet-like photosensitive material 12 (hereinafter referred to as “the pattern forming material”) in which at least the photosensitive layer in the pattern forming material is laminated. A flat moving stage 14 that holds the photosensitive layer 12 by adsorption to the surface. Two guides 20 extending along the stage moving direction are installed on the upper surface of the thick plate-shaped installation table 18 supported by the four legs 16. The stage 14 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by the guide 20 so as to be reciprocally movable. The pattern forming apparatus 10 is provided with a stage driving device (not shown) that drives the stage 14 along the guide 20.

  A U-shaped gate 22 is provided at the center of the installation base 18 so as to straddle the movement path of the stage 14. Each end of the U-shaped gate 22 is fixed to both side surfaces of the installation base 18. A scanner 24 is provided on one side across the gate 22, and a plurality of (for example, two) sensors 26 that detect the front and rear ends of the photosensitive material 12 are provided on the other side. The scanner 24 and the sensor 26 are respectively attached to the gate 22 and fixedly arranged above the moving path of the stage 14. The scanner 24 and the sensor 26 are connected to a controller (not shown) that controls them.

  Here, for explanation, an X axis and a Y axis orthogonal to each other are defined in a plane parallel to the surface of the stage 14 as shown in FIG.

  A slit formed in a “<” shape that opens in the direction of the X-axis at the upstream edge (hereinafter sometimes simply referred to as “upstream”) along the scanning direction of the stage 14. 10 are formed at equal intervals. Each slit 28 includes a slit 28 a located on the upstream side and a slit 28 b located on the downstream side. The slit 28a and the slit 28b are orthogonal to each other, and the slit 28a has an angle of −45 degrees and the slit 28b has an angle of +45 degrees with respect to the X axis.

  The position of the slit 28 is substantially coincident with the center of the exposure head 30. Further, the size of each slit 28 is set to sufficiently cover the width of the exposure area 32 by the corresponding exposure head 30. Further, the position of the slit 28 may be substantially coincident with the center position of the overlapping portion between the adjacent exposed regions 34. In this case, the size of each slit 28 is set so as to sufficiently cover the width of the overlapping portion between the exposed regions 34.

  In the position below each slit 28 inside the stage 14, single cell type light detection as a light spot position detecting means for detecting a light spot as a pixel unit in a used pixel part designation process described later. A vessel (not shown) is incorporated. In addition, each photodetector is connected to an arithmetic unit (not shown) as a pixel part selection means for selecting the pixel part in the used pixel part specifying process described later.

  The operation form of the pattern forming apparatus at the time of exposure may be a form in which exposure is continuously performed while constantly moving the exposure head, or each movement destination position while the exposure head is moved stepwise. The exposure head may be stationary to perform the exposure operation.

<< Exposure head >>
Each exposure head 30 is connected to the scanner 24 so that each pixel portion (micromirror) row direction of an internal digital micromirror device (DMD) 36 described later forms a predetermined set inclination angle θ with the scanning direction. It is attached. For this reason, the exposure area 32 by each exposure head 30 is a rectangular area inclined with respect to the scanning direction. As the stage 14 moves, a strip-shaped exposed region 34 is formed in the photosensitive layer 12 for each exposure head 30. In the example shown in FIGS. 2 and 3B, the scanner 24 includes ten exposure heads arranged in a substantially matrix of 2 rows and 5 columns.
In the following description, when the individual exposure heads arranged in the mth row and the nth column are indicated, the exposure head 30 _mn is indicated, and exposure by the individual exposure heads arranged in the mth row and the nth column is performed. When an area is indicated, it is expressed as an exposure area 32 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads 30 in each row arranged in a line so that each of the strip-shaped exposed regions 34 partially overlaps the adjacent exposed region 34 is In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice in this embodiment). Therefore, can not be exposed portion between the exposure area _{32 11} in the first row and the exposure area _{32 12,} it can be exposed by the second row of the exposure area _{32 21.}

  As shown in FIGS. 4 and 5, each of the exposure heads 30 includes a light modulation unit (spatial light modulation element that modulates each pixel unit) that modulates incident light for each pixel unit according to image data. DMD36 (manufactured by Texas Instruments, USA). The DMD 36 is connected to a controller serving as a pixel part control unit including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the use area on the DMD 36 for each exposure head 30 based on the input image data. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 36 for each exposure head 30 based on the control signal generated by the image data processing unit.

  As shown in FIG. 4, on the light incident side of the DMD 36, there is provided a laser emission portion in which the emission end portion (light emission point) of the optical fiber is arranged in a line along the direction that coincides with the long side direction of the exposure area 32. The fiber array light source 38, the lens system 40 for correcting the laser light emitted from the fiber array light source 38 and condensing it on the DMD, and the mirror 42 for reflecting the laser light transmitted through the lens system 40 toward the DMD 36 Arranged in order. In FIG. 4, the lens system 40 is schematically shown.

  As shown in detail in FIG. 5, the lens system 40 has a pair of combination lenses 44 that collimate the laser light emitted from the fiber array light source 38, and the light quantity distribution of the collimated laser light becomes uniform. A pair of combination lenses 46 to be corrected in this way, and a condensing lens 48 that condenses the laser light whose light quantity distribution has been corrected on the DMD 36.

  Further, on the light reflection side of the DMD 36, a lens system 50 that images the laser light reflected by the DMD 36 on the exposed surface of the photosensitive layer 12 is disposed. The lens system 50 includes two lenses 52 and 54 arranged so that the DMD 36 and the exposed surface of the photosensitive layer 12 have a conjugate relationship.

  In the present embodiment, the laser light emitted from the fiber array light source 38 is substantially magnified five times, and then the light from each micromirror on the DMD 36 is reduced to about 5 μm by the lens system 50. Is set to

-Light modulation means-
The light modulating means has n (where n is a natural number of 2 or more) two-dimensionally arranged image elements, and can control the image elements according to the pattern information. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, a spatial light modulation element is preferable.

  Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and modulates transmitted light by an electro-optic effect. An optical element (PLZT element), a liquid crystal optical shutter (FLC), etc. are mentioned, Among these, DMD is mentioned suitably.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 6, the DMD 36 is a mirror device in which a large number of micromirrors 58 are arranged in a lattice pattern on a SRAM cell (memory cell) 56 as a pixel portion constituting each pixel (pixel). . In this embodiment, a DMD 36 in which 1024 columns × 768 rows of micromirrors 58 are arranged is used. Among these, the micromirrors 58 that can be driven by a controller connected to the DMD 36, that is, usable micromirrors 58 are 1024 columns × 256 rows. Suppose only. The data processing speed of the DMD 36 is limited, and the modulation speed per line is determined in proportion to the number of micromirrors to be used. Thus, by using only some of the micromirrors in this way, Modulation speed increases. Each micromirror 58 is supported by a support column, and a material having high reflectivity such as aluminum is deposited on the surface thereof. In the present embodiment, the reflectance of each micromirror 58 is 90% or more, and the arrangement pitch thereof is 13.7 μm in both the vertical direction and the horizontal direction. The SRAM cell 56 is of a silicon gate CMOS manufactured in a normal semiconductor memory manufacturing line via a support including a hinge and a yoke, and the whole is configured monolithically (integrated).

  When an image signal representing the density of each point constituting a desired two-dimensional pattern in binary is written in the SRAM cell (memory cell) 56 of the DMD 36, each micromirror 58 supported by the column is centered on the diagonal line. As shown in FIG. 1, the inclination is inclined to ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 36 is disposed. FIG. 7A shows a state in which the micromirror 58 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 58 is tilted to −α degrees in the off state. In this way, by controlling the inclination of the micromirror 58 in each pixel of the DMD 36 as shown in FIG. 6 in accordance with the image signal, the laser light B incident on the DMD 36 moves in the inclination direction of each micromirror 58. Reflected.

  FIG. 6 shows an example in which a part of the DMD 36 is enlarged and each micromirror 58 is controlled to + α degrees or α degrees. The on / off control of each micromirror 58 is performed by the controller connected to the DMD 36. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 58 travels.

-Light irradiation means-
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light irradiated from the light irradiation means, for example, when light irradiation is performed through a support, transmits the support and activates the used photopolymerization initiating compound or sensitizer. Examples include electromagnetic waves, ultraviolet to visible light, electron beams, X-rays, and laser beams. Among these, laser beams are preferable, and a laser that combines two or more lights (hereinafter sometimes referred to as a “combined laser”). Is more preferable. Even when light irradiation is performed after the support is peeled off, the same light can be used.

As a wavelength of the ultraviolet to visible light, for example, 300 to 1500 nm is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 400 nm-450 nm is especially preferable.

  Examples of means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and collective optics for condensing the laser beams respectively emitted from the plurality of lasers and coupling them to the multimode optical fiber. Means having a system are preferred.

Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.
As shown in FIG. 8, the fiber array light source 38 includes a plurality of (for example, 14) laser modules 60, and one end of a multimode optical fiber 62 is coupled to each laser module 60. An optical fiber 64 having a cladding diameter smaller than that of the multimode optical fiber 62 is coupled to the other end of the multimode optical fiber 62. As shown in detail in FIG. 9, seven ends of the optical fiber 64 opposite to the multimode optical fiber 62 are arranged along the direction orthogonal to the scanning direction, and these are arranged in two rows to form the laser emitting unit 66. Is configured.

  As shown in FIG. 9, the laser emitting portion 66 constituted by the end portion of the optical fiber 64 is sandwiched and fixed between two support plates 68 having a flat surface. Moreover, it is desirable that a transparent protective plate such as glass is disposed on the light emitting end face of the optical fiber 64 for protection. The light exit end face of the optical fiber 64 has a high light density and is likely to collect dust and easily deteriorate. However, by arranging the protective plate as described above, it is possible to prevent the dust from adhering to the end face and to delay the deterioration. Can do.

  For example, as shown in FIG. 25, such an optical fiber is formed by coaxially connecting an optical fiber 64 having a length of 1 to 30 cm with a small cladding diameter at the tip portion on the laser light emission side of a multimode optical fiber 62 having a large cladding diameter. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 64 is fused and joined to the outgoing end face of the multimode optical fiber 62 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 64 a of the optical fiber 64 is the same as the diameter of the core 62 a of the multimode optical fiber 62.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused with an optical fiber having a small cladding diameter may be coupled to the output end of the multimode optical fiber 62 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 64 may be referred to as an emission end portion of the multimode optical fiber 62.

  The multimode optical fiber 62 and the optical fiber 64 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 62 and the optical fiber 64 are step index type optical fibers, and the multimode optical fiber 62 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 64 has a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm. However, the smaller the clad diameter, the deeper the focal depth, so the clad diameter of the optical fiber is preferably 80 μm or less, more preferably 60 μm or less. 40 μm or less is more preferable. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 64 is preferably 10 μm or more.

  The laser module 60 is composed of a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6 arranged on the heat block 110, And LD7, collimator lenses L1, L2, L3, L4, L5, L6, and L7 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 200, and one multimode. And an optical fiber 62. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is also all the same (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 27 and 28, the combined laser light source is housed in a box-shaped package 400 having an upper opening together with other optical elements. The package 400 includes a package lid 410 created so as to close the opening. After the degassing process, a sealing gas is introduced, and the package 400 and the package lid are closed by closing the opening of the package 400 with the package lid 410. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by the reference numeral 410.

  A base plate 420 is fixed to the bottom surface of the package 400, and the heat block 110, a condensing lens holder 450 that holds the condensing lens 200, and the multimode optical fiber 62 are disposed on the top surface of the base plate 420. A fiber holder 460 that holds the incident end is attached. The exit end of the multimode optical fiber 62 is drawn out of the package from an opening formed in the wall surface of the package 400.

  A collimator lens holder 440 is attached to the side surface of the heat block 110, and the collimator lenses L1 to L7 are held. An opening is formed in the lateral wall surface of the package 400, and a wiring 470 for supplying a driving current to the GaN semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 28, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens L7 is numbered among the plurality of collimator lenses. is doing.

  FIG. 29 shows a front shape of a mounting portion of the collimator lenses L1 to L7. Each of the collimator lenses L <b> 1 to L <b> 7 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses L1 to L7 are closely arranged in the light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (left-right direction in FIG. 29).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a state parallel to the active layer and a divergence angle in a direction perpendicular to the active layer, for example, 10 ° and 30 °. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses L1 to L7 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses L1 to L7 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. In addition, each of the collimator lenses L1 to L7 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 200 is formed by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane in parallel planes, and is long in the arrangement direction of the collimator lenses L1 to L7, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. The condenser lens 200 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 200 is also formed by molding resin or optical glass, for example.

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. A pattern forming apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.

  In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the entrance end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Moreover, as a light irradiation means provided with a plurality of light emitting points, for example, as shown in FIG. 30, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on a heat block 110. An array can be used. Further, a chip-shaped multi-cavity laser 110 shown in FIG. 31A in which a plurality of (for example, five) light emitting points 111a are arranged in a predetermined direction is known. Since the multicavity laser 111 can arrange the light emitting points with high positional accuracy as compared with the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, as the number of light emitting points increases, the multi-cavity laser 111 is likely to be bent at the time of laser manufacture. Therefore, the number of light emitting points 111a is preferably 5 or less.

  As the light irradiation means, as shown in FIG. 31B, a plurality of multi-cavity lasers 111 are arranged on the heat block 110 in the same direction as the arrangement direction of the light emitting points 111a of each chip. A multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 32, a combined laser light source including a chip-shaped multicavity laser 111 having a plurality of (for example, three) emission points 111a can be used. The combined laser light source includes a multi-cavity laser 111, a single multi-mode optical fiber 62, and a condenser lens 200. The multicavity laser 111 can be composed of, for example, a GaN laser diode having an oscillation wavelength of 405 nm.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the multicavity laser 111 is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 111 a of the multicavity laser 111 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 62, and a focal point substantially equal to the core diameter of the multimode optical fiber 62 is formed as the condenser lens 200. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multicavity laser 111 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multimode optical fiber 62 can be increased. it can.

  As shown in FIG. 33, a multi-cavity laser 111 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 111 are equidistant from each other on the heat block 110. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 111 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 111a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 111, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111 a of the plurality of multi-cavity lasers 111 is condensed in a predetermined direction by the rod lens 113 and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is collected by the condenser lens 200 and enters the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. As shown in FIGS. 34A and 34B, this combined laser light source has a heat block 182 having an L-shaped cross section in the optical axis direction mounted on a substantially rectangular heat block 180 and is housed between two heat blocks. A space is formed. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 111 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 111a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 111, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 111a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the divergence angle of the laser beam is large (the fast axis direction), and the width direction of each collimating lens is the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser beam emitting side of the collimating lens array 184, there is one multimode optical fiber 62 and a condensing lens 200 that condenses and couples the laser beam to the incident end of the multimode optical fiber 62. Is arranged.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 111a of the plurality of multi-cavity lasers 111 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is collected by the optical lens 200 and is incident on the core 62 a of the multimode optical fiber 62. The laser light incident on the core 62a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be configured, so that it is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

  A laser module in which each of the combined laser light sources is housed in a casing and the emission end portion of the multimode optical fiber 62 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

<< Used pixel part designation means >>
The used pixel part specifying means includes a light spot position detecting means for detecting the position of a light spot on a surface to be exposed as a pixel unit, and N-fold exposure based on a detection result by the light spot position detecting means. It is preferable to include at least a pixel part selection unit that selects a pixel part to be used for the realization.
Hereinafter, an example of a method for designating a pixel part used for N-exposure by the used pixel part designation unit will be described.

(1) Method for Specifying Picture Element Portions Used in Single Exposure Head In the present embodiment (1), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12, and each exposure head 30. A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the mounting angle error and realizing ideal double exposure.

The set inclination angle θ in the column direction of the image element (micromirror 58) with respect to the scanning direction of the exposure head 30 can be used as long as there is no mounting angle error of the exposure head 30 or the like. It is assumed that an angle slightly larger than the angle θ _ideal that is exactly double exposure using 256 lines of pixel parts is adopted.
This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
It becomes. In the present embodiment (1), since s = 256 and N = 2 as described above, the angle θ _ideal is about 0.45 degrees according to Equation 3. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

  FIG. 10 illustrates an example of unevenness in a pattern on an exposed surface due to the influence of an attachment angle error of one exposure head 30 and pattern distortion in the pattern forming apparatus 10 that is initially adjusted as described above. FIG. In the following drawings and description, the light spot in the m-th row is represented by r (m) with respect to the light spot generated by each pixel part (micromirror) and constituting the exposure area on the exposed surface. ), The light spot in the nth column is denoted as c (n), and the light spot in the mth row and the nth column is denoted as P (m, n).

The upper part of FIG. 10 shows a pattern of light spot groups from the usable micromirrors 58 projected onto the exposed surface of the photosensitive material 12 with the stage 14 being stationary, and the lower part is the upper part. 2 shows the state of the exposure pattern formed on the surface to be exposed when the stage 14 is moved and continuous exposure is performed in the state where the pattern of light spots as shown in FIG.
In FIG. 10, for convenience of explanation, the exposure pattern of the odd-numbered columns of the usable micromirrors 58 and the exposure pattern of the even-numbered columns are shown separately. However, the actual exposure patterns on the exposed surface are shown in FIG. Two exposure patterns are superimposed.

In the example of FIG. 10, as a result of adopting the set inclination angle θ slightly larger than the angle θ _ideal , and because it is difficult to finely adjust the mounting angle of the exposure head 30, the actual mounting angle and the above As a result of the error in the set inclination angle θ, density unevenness occurs in any region on the exposed surface. Specifically, in both the exposure pattern by the odd-numbered micromirrors and the exposure pattern by the even-numbered micromirrors, it is ideal in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows. Overexposure occurs with respect to double exposure, resulting in a redundant drawing area and uneven density.

Furthermore, the example of FIG. 10 is an example of pattern distortion appearing on the surface to be exposed, and “angular distortion” occurs in which the inclination angle of each pixel row projected on the surface to be exposed is not uniform. Causes of such angular distortion include various aberrations and alignment deviations of the optical system between the DMD 36 and the exposed surface, distortion of the DMD 36 itself, micromirror placement errors, and the like.
The angular distortion appearing in the example of FIG. 10 is a distortion in which the tilt angle with respect to the scanning direction is smaller in the left column of the figure and larger in the right column of the figure. As a result of this angular distortion, the overexposed area is smaller on the exposed surface shown on the left side of the figure and larger on the exposed surface shown on the right side of the figure.

In order to reduce the density unevenness in the overlapped exposure region on the exposed surface formed by a plurality of pixel part rows as described above, a set of the slit 28 and the photodetector is used as the light spot position detecting means. The actual inclination angle θ ′ is specified for each exposure head 30, and based on the actual inclination angle θ ′, the arithmetic unit connected to the photodetector as the pixel portion selection unit is used for actual exposure. A process of selecting a micromirror to be used is performed.
The actual inclination angle θ ′ is based on at least two light spot positions detected by the light spot position detection means, and the light spot column direction on the surface to be exposed and the scanning direction of the exposure head when the exposure head is tilted. It is specified by the angle formed by.
Hereinafter, the specification of the actual inclination angle θ ′ and the used pixel selection process will be described with reference to FIGS.

-Specification of actual inclination angle θ'-
FIG. 11 is a top view showing the positional relationship between the exposure area 32 by one DMD 36 and the corresponding slit 28. The size of the slit 28 is set to sufficiently cover the width of the exposure area 32.
In the example of the present embodiment (1), the angle formed by the 512th light spot row positioned substantially at the center of the exposure area 32 and the scanning direction of the exposure head 30 is measured as the actual inclination angle θ ′. . Specifically, the micromirror 58 in the first row and the 512th column and the micromirror 58 in the 256th row and the 512th column on the DMD 36 are turned on, and the light spots on the exposure surface corresponding to each of the micromirrors 58 are turned on. The positions of P (1,512) and P (256,512) are detected, and the angle formed by the straight line connecting them and the scanning direction of the exposure head is specified as the actual inclination angle θ ′.

FIG. 12 is a top view illustrating a method for detecting the position of the light spot P (256, 512).
First, in a state where the micromirror 58 in the 256th row and the 512th column is turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 512) is changed. The slit 28 is positioned at an arbitrary position so as to be between the upstream slit 28a and the downstream slit 28b. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 12 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 12, the stage 14 is stopped when the light at the light spot P (256, 512) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 512).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 512) on the surface to be exposed are X = X0 + (Y1-Y2) / 2, Y = (Y1 + Y2) / 2. Determine by calculation. By the same measurement, coordinates indicating the position of P (1,512) are also determined, an inclination angle formed by a straight line connecting the respective coordinates and the scanning direction of the exposure head 30 is derived, and this is obtained as an actual inclination angle θ ′. As specified.

-Selection of used pixel part-
Using the actual inclination angle θ ′ thus specified, the arithmetic unit connected to the photodetector is expressed by the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived, and the first to T-th row micromirrors on the DMD 36 are selected as micromirrors that are actually used during the main exposure. In this way, in the exposure region near the 512th column, a micromirror that minimizes the total area of the overexposed region and the underexposed region with respect to the ideal double exposure is actually obtained. It can be selected as a micromirror to be used for.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the overexposed region and does not produce an underexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.
It is also possible to derive the maximum natural number equal to or less than the value t. In that case, in the exposure region near the 512th column, a micromirror that minimizes the area of the underexposed region and does not produce an overexposed region with respect to ideal double exposure. It can be selected as a micromirror to be actually used.

FIG. 13 shows how the unevenness on the exposed surface shown in FIG. 10 is improved in the exposure performed using only the light spot generated by the micromirror selected as the micromirror to be actually used as described above. It is explanatory drawing which showed what was done.
In this example, it is assumed that T = 253 is derived as the natural number T and the micromirrors in the first row to the 253rd row are selected. For the micromirrors in the 254th to 256th rows that are not selected, the pixel part control means sends a signal to set the angle of the always-off state, and these micromirrors are substantially Not involved in exposure. As shown in FIG. 13, in the exposure region near the 512th column, overexposure and underexposure are almost completely eliminated, and uniform exposure very close to ideal double exposure is realized.

On the other hand, in the left region of FIG. 13 (near c (1) in the figure), the inclination angle of the light spot sequence on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. This is smaller than the inclination angle of the light beam row in the region. Therefore, in the exposure using only the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, the ideal double pattern is used for each of the even-numbered exposure pattern and the odd-numbered exposure pattern. An area that is underexposed with respect to the exposure is slightly generated.
However, in the actual exposure pattern formed by overlaying the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the regions where the exposure amount is insufficient are complemented with each other, and the exposure unevenness due to the angular distortion is double-exposed. The effect of offsetting can be minimized.

Further, in the region on the right side of FIG. 13 (near c (1024) in the figure), the inclination angle of the light beam on the exposed surface is near the center (near c (512) in the figure) due to the angular distortion. It is larger than the inclination angle of the light beam row in the region. Therefore, in the exposure with the micromirror selected based on the actual inclination angle θ ′ measured with c (512) as a reference, as shown in the figure, there is an overexposed region with respect to the ideal double exposure. It will occur slightly.
However, in the actual exposure pattern formed by superimposing the exposure pattern of the odd-numbered columns and the exposure pattern of the even-numbered columns shown in the figure, the overexposed regions are complemented with each other, and the density unevenness due to the angular distortion is caused by the double exposure. The effect of offsetting can be minimized.

In the present embodiment (1), as described above, the actual inclination angle θ ′ of the 512th ray array is measured, and based on the T derived from the equation (4) using the actual inclination angle θ ′. The micro-mirror 58 to be used is selected. However, as a method of specifying the actual inclination angle θ ′, a plurality of actual directions formed by the column direction (light spot column) of the plurality of image elements and the scanning direction of the exposure head are used. Each of the tilt angles is measured, and any one of the average value, median value, maximum value, and minimum value is specified as an actual tilt angle θ ′. It is good also as a form to select.
When the average value or the median value is set to the actual inclination angle θ ′, it is possible to realize exposure with a good balance between an overexposed area and an underexposed area with respect to an ideal N-fold exposure. For example, the total area of the overexposed region and the underexposed region is minimized, and the number of pixel units (number of light spots) in the overexposed region and the underexposed region are drawn. It is possible to realize exposure such that the number of prime units (number of light spots) is equal.
Further, if the maximum value is set to the actual inclination angle θ ′, it is possible to realize an exposure that places more importance on eliminating an overexposed region with respect to an ideal N double exposure, for example, an underexposure. It is possible to realize exposure that minimizes the area of the region and does not generate an overexposed region.
Further, if the minimum value is set to the actual inclination angle θ ′, it is possible to realize exposure that places more importance on eliminating underexposed areas with respect to ideal N-fold exposure, for example, overexposure. It is possible to realize exposure that minimizes the area of the region and does not cause a region that is underexposed.

On the other hand, the specification of the actual inclination angle θ ′ is not limited to the method based on the positions of at least two light spots in the same pixel part row (light spot row). For example, the angle obtained from the position of one or more light spots in the same pixel part sequence c (n) and the position of one or more light spots in the row near the c (n), The actual inclination angle θ ′ may be specified.
Specifically, one light spot position in c (n) and one or a plurality of light spot positions included in a light spot row on a straight line and in the vicinity along the scanning direction of the exposure head are detected. The actual inclination angle θ ′ can be obtained from the position information. Further, the angle obtained based on the positions of at least two light spots (for example, two light spots arranged so as to straddle c (n)) in the light spot array in the vicinity of the c (n) line is an actual inclination. The angle θ ′ may be specified.

  As described above, according to the specification method of the used picture element portion of the present embodiment (1) using the pattern forming apparatus 10, resolution variation and density unevenness due to the influence of the mounting angle error of each exposure head and pattern distortion are eliminated. It is possible to reduce and realize an ideal N double exposure.

(2) Method for designating used pixel parts between a plurality of exposure heads <1>
In the present embodiment (2), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by the plurality of exposure heads 30. In the intermittent region, the variation in resolution and density unevenness due to the deviation from the ideal state of the relative position of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction are reduced; A description will be given of a method for designating a used pixel portion for realizing ideal double exposure.

As the set inclination angle θ of each exposure head 30, that is, each DMD 36, the usable pixel portion micromirror 58 of 1024 columns × 256 rows is used if there is no ideal mounting angle error of the exposure head 30. Then, it is assumed that an angle θ _ideal that is exactly double exposure is adopted.
This angle θ _ideal is obtained from the above equations 1 to 3 in the same manner as in the above embodiment (1). In the present embodiment (2), it is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 becomes this angle θ _ideal .

FIG. 14 shows the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state in the pattern forming apparatus 10 initially adjusted as described above. It is explanatory drawing which showed the example of the density nonuniformity which arises in the pattern on a to-be-exposed surface by the influence. The displacement of the relative position of each exposure head in the X-axis direction can occur because it is difficult to finely adjust the relative position between the exposure heads.

14 is projected onto the exposed surface of the photosensitive material 12 in a state where the stage 14 is stationary, the light spot group from the usable micromirror 58 of the DMD 36 of the exposure heads 30 ₁₂ and 30 _21. It is the figure which showed these patterns. The lower part of FIG. 14 shows the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing. The state is shown for exposure areas 32 ₁₂ and 32 ₂₁ .
In FIG. 14, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

In the example of FIG. 14, the exposure pattern by the pixel column group A and the pixel column group B as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ in the X-axis direction from the ideal state. In both of the above exposure patterns, a portion where the exposure amount is larger than the ideal double exposure state occurs in the connection area between the heads in the exposure areas 32 ₁₂ and 32 ₂₁ .

In order to reduce density unevenness appearing in the inter-head connecting region formed on the exposed surface by the plurality of exposure heads as described above, in this embodiment (2), a slit is used as the light spot position detecting means. 28 and a set of photodetectors, the positions of some of the light spots constituting the connecting area between the heads formed on the exposed surface among the light spot groups from the exposure heads 30 ₁₂ and 30 _21. Detect (coordinates). Based on the position (coordinates), processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to the photodetector as the pixel portion selection means.

-Detection of position (coordinates)-
FIG. 15 is a top view showing the positional relationship between the exposure areas 32 ₁₂ and 32 ₂₁ similar to those in FIG. 14 and the corresponding slits 28. The size of the slit 28 is large enough to cover the width of the overlapping portion between the exposed areas 34 by the exposure heads 30 ₁₂ and 30 ₂₁ , that is, the slit 28 is formed on the exposed surface by the exposure heads 30 ₁₂ and 30 _21. The size is sufficient to cover the connection area between the heads.

Figure 16 is a top view for explaining a detection method of detecting the position of a point P of the exposure area _{32 21} as an example (256, 1024).
First, with the micromirror in the 256th row and the 1024th column turned on, the stage 14 is slowly moved to relatively move the slit 28 along the Y-axis direction, and the light spot P (256, 1024) is upstream. The slit 28 is positioned at an arbitrary position so as to be between the slit 28a on the side and the slit 28b on the downstream side. At this time, the coordinates of the intersection of the slit 28a and the slit 28b are (X0, Y0). The value of this coordinate (X0, Y0) is determined and recorded from the movement distance of the stage 14 to the position indicated by the drive signal given to the stage 14 and the known X-direction position of the slit 28. .

  Next, the stage 14 is moved, and the slit 28 is relatively moved to the right in FIG. 16 along the Y axis. Then, as indicated by the two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the left slit 28b and is detected by the photodetector. The coordinates (X0, Y1) of the intersection of the slit 28a and the slit 28b at this time are recorded as the position of the light spot P (256, 1024).

  Next, the stage 14 is moved in the opposite direction, and the slit 28 is relatively moved to the left in FIG. 16 along the Y axis. Then, as indicated by a two-dot chain line in FIG. 16, the stage 14 is stopped when the light at the light spot P (256, 1024) passes through the right slit 28a and is detected by the photodetector. The coordinates (X0, Y2) of the intersection of the slit 28a and the slit 28b at this time are recorded as the light spot P (256, 1024).

  From the above measurement results, the coordinates (X, Y) indicating the position of the light spot P (256, 1024) on the exposed surface are calculated as X = X0 + (Y1−Y2) / 2, Y = (Y1 + Y2) / 2. Determined by

-Identification of unused pixel parts-
In the example of FIG. 14, first, the position of the point P of the exposure area _{32 12} (256,1) is detected by a set of slits 28 and a photodetector as the light spot position detecting unit. Subsequently, the position of each light spot on the 256 line of light spots row r of the exposure area _{32 21 (256), P (} 256,1024), to detect the P (256,1023) ··· and order periodically, where the exposure area _{32 21} of point P indicating the exposure area _{32 12} point P (256,1) larger X coordinate than the (256, n) is detected, and terminates the detecting operation. Then, the micro mirrors corresponding to light spots constituting the c (1024) from the light spot column c of the exposure area 32 ₂₁ (n + 1), specifies as a micro-mirror is not used during the exposure (unused pixel parts).
For example, in FIG. 14, the exposure area _{32 21} point P (256,1020) is shows a larger X coordinate than the point P of the exposure area _{32 12} (256,1) of the exposure area _{32 21} spot If P (256,1020) is that the detection operation at the detected ended, the light spots constituting the first 1024 lines from the 1021 line of exposure area _{32 21,} corresponding to the portion 70 covered with hatched in FIG. 17 The corresponding micromirror is identified as a micromirror that is not used during the main exposure.

Next, the number N of the N multiple exposure, the position of the point P of the exposure area _{32 12} (256, N) is detected. In this embodiment (2), since N = 2, the position of the light spot P (256, 2) is detected.
Then, among the light spot columns of the exposure area 32 _21, except those identified as light spots string corresponding to the micromirrors is not used during the exposure in the above, the position of the light spot constituting the rightmost 1020 column a, P (1,1020) in order from P (1,1020), P (2,1020 ) ··· and continue to detection, greater than the point P of the exposure area _{32 12} (256,2) X When the light spot P (m, 1020) indicating the coordinates is detected, the detection operation is terminated.
Thereafter, the connected operational devices to said light detector, and X-coordinate of the exposure area _{32 12} of the light spot P (256, two), point P of the exposure area _{32 21} (m, 1020) and P (m- and X-coordinate of 1,1020) are compared, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m, 1020) is closer to the X coordinate of the point P in the exposure area _{32 12} (256, 2) a micro mirror corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020) is identified as a micro-mirror is not used during the exposure.
Also, if the direction of the X coordinate of the point P of the exposure area _{32 21} (m-1,1020) is close to the X-coordinate of the point P in the exposure area _{32 12} (256, 2), the light of the exposure area _{32 21} Micromirrors corresponding to points P (1, 1020) to P (m−2, 1020) are specified as micromirrors that are not used for the main exposure.
Furthermore, the position of the point P of the exposure area _{32 12 (256, N-1} ) That point P (256,1), the position of each point constituting the first 1019 column is the next row of the exposure area _{32 21} The same detection process and identification of micromirrors that are not used are also performed.

  As a result, for example, micromirrors corresponding to the light spots that form the shaded area 72 in FIG. 17 are added as micromirrors that are not used during actual exposure. These micromirrors are always signaled to set the micromirror angle to the off-state angle, and these micromirrors are substantially not used for exposure.

As described above, the micromirrors that are not used at the time of actual exposure are identified, and the micromirrors that are not used at the time of actual exposure are selected as the micromirrors that are used at the time of actual exposure, whereby the exposure areas 32 ₁₂ and 32 ₂₁ In the connecting area between the heads, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure can be minimized. As shown in the lower part of FIG. Uniform exposure extremely close to double exposure can be realized.

In the above example, upon the particular light spots constituting the regions 72 covered with hatched in FIG. 17, the X coordinate of the point P in the exposure area _{32 12} (256, 2), the exposure area _{32 21} of the light spot P (m, 1020) and P (m-1,1020) without comparison of the X-coordinate of the immediately, P from point P of the exposure area _{32 21 (1,1020) (m-} 2 , 1020) may be specified as a micromirror that is not used during the main exposure. In that case, in the connecting area between the heads, a micromirror is actually used that minimizes the area of an overexposed area with respect to an ideal double exposure and does not cause an underexposed area. It can be selected as a micromirror.
Further, the micro-mirrors corresponding to P (m-1,1020) from point P of the exposure area _{32 21} (1,1020), it may be specified as micro mirrors not used in this exposure. In that case, in the connecting region between the heads, a micromirror is actually used in which the area of the region that is underexposed with respect to the ideal double exposure is minimized and the region that is not overexposed does not occur. It can be selected as a micromirror.
Further, in the connecting area between the heads, the number of pixel units (the number of light spots) in an area that is overexposed with respect to an ideal double drawing and the number of pixel units (the number of light spots) in an area that is underexposed. It is good also as selecting the micromirror actually used so that it may become equal.

  As described above, according to the specification method of the used pixel part of the present embodiment (2) using the pattern forming apparatus 10, the resolution variation caused by the relative position shift in the X-axis direction of the plurality of exposure heads Density unevenness can be reduced, and ideal N-fold exposure can be realized.

(3) Specification method of used pixel parts between a plurality of exposure heads <2>
In this embodiment (3), the pattern forming apparatus 10 performs double exposure on the photosensitive material 12 and is a head that is an overlapped exposure region on the exposed surface formed by a plurality of exposure heads 30. In the intermittent region, the deviation of the relative positions of the two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the X-axis direction from the ideal state, the mounting angle error of each exposure head, and the two exposure heads A description will be given of a method for designating a used pixel part for reducing the variation in resolution and density unevenness caused by the relative mounting angle error between them and realizing ideal double exposure.

As the set tilt angle of each exposure head 30, that is, each DMD 36, in an ideal state where there is no mounting angle error of the exposure head 30, a usable 1024 column × 256 row pixel element (micromirror 58) is provided. It is assumed that an angle slightly larger than the angle θ _ideal that is used for exactly double exposure is adopted.
This angle θ _ideal is a value obtained in the same manner as the above embodiment (1) using the above equations 1 to 3, and in this embodiment, s = 256 and N = 2 as described above. The angle θ _ideal is about 0.45 degrees. Therefore, for example, an angle of about 0.50 degrees may be employed as the set inclination angle θ. It is assumed that the pattern forming apparatus 10 is initially adjusted so that the mounting angle of each exposure head 30, that is, each DMD 36 is close to the set inclination angle θ within an adjustable range.

FIG. 18 shows a mounting angle error of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) in the pattern forming apparatus 10 in which the mounting angle of each exposure head 30, that is, each DMD 36 is initially adjusted as described above, the influence of the deviation of the relative mounting angle error and the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ is an explanatory view showing an example of unevenness that occurs in the pattern on the exposed surface.

In the example of FIG. 18, as in the example of FIG. 14, as a result of the shift of the relative positions of the exposure heads 30 ₁₂ and 30 _{21 in} the X-axis direction, exposure by every other light spot group (pixel column groups A and B) is performed. In both exposure patterns 32 ₁₂ and 32 ₂₁ , the exposure amount overlaps on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface of the exposure areas 32 ₁₂ and 32 ₂₁ , which is more than the ideal double exposure state. A region 74 is generated, which causes uneven density.
Furthermore, in the example of FIG. 18, it is difficult to finely adjust the result of setting the tilt angle θ of each exposure head to be slightly larger than the angle θ _ideal satisfying the formula (1) and the mounting angle of each exposure head. Therefore, as a result of the actual mounting angle deviating from the set inclination angle θ, even in regions other than the exposure region overlapping on the coordinate axis perpendicular to the scanning direction of the exposure head on the exposed surface, In the connection region between the pixel part columns, which is an overlapped exposure region on the exposed surface, formed by a plurality of pixel part columns, both in the exposure pattern by every other light spot group (pixel column group A and B). A region 76 that is overexposed than the ideal double exposure state is generated, and this causes further density unevenness.

In this embodiment (3), first, the use pixel selection process for reducing the uneven density due to the influence of the deviation of the mounting angle error and relative mounting angle of the exposure heads 30 ₁₂ and 30 _21.
Specifically, a set of a slit 28 and a photodetector is used as the light spot position detecting means, and an actual inclination angle θ ′ is specified for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the actual inclination angle θ ′ is set. Based on this, it is assumed that processing for selecting a micromirror to be used for actual exposure is performed using an arithmetic unit connected to a photodetector as the pixel part selection means.

-Specification of actual inclination angle θ'-
The actual inclination angle θ ′ is specified with respect to the positions of the light spots P (1, 1) and P (256, 1) in the exposure area 32 ₁₂ for the exposure head 30 _{12 and in the} exposure area 32 ₂₁ for the exposure head 30 ₂₁ . The positions of the light spots P (1,1024) and P (256,1024) are detected by the combination of the slit 28 and the photodetector used in the above-described embodiment (2), and the inclination angle of the straight line connecting them. And the angle formed by the scanning direction of the exposure head.

-Identification of unused pixel parts-
The arithmetic device connected to the photodetector using the actual inclination angle θ ′ thus specified is similar to the following equation 4 similar to the arithmetic device in the embodiment (1) described above.
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the above relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ , and the micromirrors in the (T + 1) th to 256th rows on the DMD 36 are not used for the main exposure. Processing to identify as a micromirror is performed.
For example, T = 254 for the exposure head _{30 12,} when T = 255 was derived for the exposure head _3O21, micro mirrors corresponding to light spots constituting the parts 78 and 80 covered with hatched in FIG. 19 These are specified as micromirrors that are not used for the main exposure. As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, the total area of the overexposed area and the underexposed area with respect to the ideal double exposure is minimized. be able to.

Here, instead of deriving the natural number closest to the above value t, the minimum natural number greater than or equal to the value t may be derived. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area where the amount is excessive and to prevent an area where the exposure amount is insufficient.
Or it is good also as deriving the maximum natural number below value t. In this case, exposure is performed for ideal double exposure in each of the exposure areas 32 ₁₂ and 32 ₂₁ other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads. It is possible to minimize the area of the insufficient region and prevent the region from being overexposed.
In each area other than the head-to-head connection area, which is an overlapping exposure area on the exposed surface formed by a plurality of exposure heads, the number of pixel units (light It is also possible to identify micromirrors that are not used during the main exposure so that the number of pixel units (the number of light points) in the underexposed region is equal to the number of points.

Thereafter, with respect to the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with diagonal lines in FIG. 19, the same processing as that of the present embodiment (3) described with reference to FIGS. In FIG. 19, the micromirrors corresponding to the light spots constituting the shaded area 82 and the shaded area 84 are identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. Not involved.

  As described above, according to the method for designating the used picture element portion of the present embodiment (3) using the pattern forming apparatus 10, the relative position shift in the X-axis direction of the plurality of exposure heads and the attachment of each exposure head Variations in resolution and density unevenness due to angle errors and relative mounting angle errors between exposure heads can be reduced, and ideal N-fold exposure can be realized.

  As described above, the method for designating the used pixel portion by the pattern forming apparatus 10 has been described in detail. However, the above-described embodiments (1) to (3) are merely examples, and various modifications can be made without departing from the scope of the present invention. It is.

  In the above embodiments (1) to (3), as a means for detecting the position of the light spot on the exposed surface, a set of the slit 28 and the single cell type photodetector is used. The present invention is not limited to this, and any form may be used. For example, a two-dimensional detector may be used.

  Further, in the above embodiments (1) to (3), the actual inclination angle θ ′ is obtained from the position detection result of the light spot on the exposed surface by the combination of the slit 28 and the photodetector, and the actual inclination angle θ ′ is obtained. The micromirrors to be used are selected based on the above, but a usable micromirror may be selected without the derivation of the actual inclination angle θ ′. Furthermore, for example, the reference exposure using all available micromirrors is performed, and the micromirror used by the operator is manually specified by checking the resolution and density unevenness by visual observation of the reference exposure results. It is included in the scope of the invention.

In addition to the angular distortion described in the above example, there are various forms of pattern distortion that can occur on the exposed surface.
As an example, as shown in FIG. 20A, there is a form of magnification distortion in which light rays from each micromirror 58 on the DMD 36 reach the exposure area 32 on the exposure surface at different magnifications.
As another example, as shown in FIG. 20B, there is a form of beam diameter distortion in which the light from each micromirror 58 on the DMD 36 reaches the exposure area 32 on the exposed surface with a different beam diameter. . These magnification distortion and beam diameter distortion are mainly caused by various aberrations and alignment deviation of the optical system between the DMD 36 and the exposed surface.
As yet another example, there is a form of light amount distortion in which light beams from the micromirrors 58 on the DMD 36 reach the exposure area 32 on the exposed surface with different light amounts. In addition to various aberrations and misalignment, this light amount distortion includes the positional dependency of the transmittance of the optical element between the DMD 36 and the exposed surface (for example, the lenses 52 and 54 in FIG. Caused by unevenness. These forms of pattern distortion also cause unevenness in resolution and density in the pattern formed on the exposed surface.

  According to the above embodiments (1) to (3), the residual elements of pattern distortion in these forms after selecting the micromirrors actually used for the main exposure are the same as the residual elements of angular distortion described above. It is possible to level out by the effect of filling by multiple exposure, and the unevenness of resolution and density can be reduced over the entire exposure area of each exposure head.

<< Reference exposure >>
As a modified example of the above embodiments (1) to (3), among available micromirrors, it corresponds to (N-1) every micromirror column or 1 / N rows of all light spot rows. A reference exposure is performed using only a group of micromirrors constituting an adjacent row, and among the micromirrors used for the reference exposure, micromirrors that are not used at the time of actual exposure are specified so that uniform exposure can be realized. It is good as well.
The result of the reference exposure by the reference exposure means is output as a sample, and the output reference exposure result is analyzed to confirm resolution variation and density unevenness and to estimate the actual inclination angle. The analysis of the result of the reference exposure may be a visual analysis by an operator.

FIG. 21 is an explanatory diagram showing an example of a form in which reference exposure is performed using only (N-1) rows of micromirrors using a single exposure head.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the odd-numbered light spot arrays indicated by the solid lines in FIG. 21A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, it is possible to specify a micromirror to be used in the main exposure by confirming variations in resolution and density unevenness, or estimating an actual inclination angle.
For example, micromirrors other than the micromirror corresponding to the light spot array shown by hatching in FIG. 21B are designated as actually used in the main exposure among the micromirrors constituting the odd light spot array. . For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and the micromirror used during the main exposure may be designated, or the same pattern as that for the odd-numbered light spot arrays may be applied. Good.
By specifying the micromirrors used in the main exposure as described above, in the main exposure using both the odd-numbered and even-numbered micromirrors, a state close to ideal double exposure can be realized.

FIG. 22 is an explanatory diagram showing an example of a form in which reference exposure is performed using only a plurality of (N-1) rows of micromirrors using a plurality of exposure heads.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference is made using only the micromirrors corresponding to the odd-numbered light spot rows of two exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction, which are indicated by solid lines in FIG. Exposure is performed, and a reference exposure result is output as a sample. Based on the output reference exposure result, the variation in resolution and density unevenness in the area other than the joint area between the heads formed on the exposed surface by the two exposure heads are confirmed, or the actual inclination angle is estimated. Thus, the micromirror to be used at the time of the main exposure can be designated.
For example, the micromirrors other than the micromirrors corresponding to the light spot rows in the area 86 shown by hatching in FIG. 22 and the shaded area 88 are among the micromirrors constituting the odd-numbered light spots, during the main exposure. Specified as actually used. For even-numbered light spot arrays, reference exposure may be performed separately in the same manner, and a micromirror used in the main exposure may be designated, or the same pattern as that for the odd-numbered pixel columns may be applied. Good.
In this way, in the main exposure using both the odd-numbered and even-numbered micromirrors by designating the micromirrors that are actually used during the main exposure, the two exposure heads form the surface to be exposed. A state close to ideal double exposure can be realized in a region other than the head-to-head connection region.

FIG. 23 is an explanatory diagram showing an example of a form in which reference exposure is performed using a single exposure head and using only micromirror groups constituting adjacent rows corresponding to 1 / N rows of the total light spot rows. It is.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only micromirrors corresponding to the light spots in the first to 128 (= 256/2) rows indicated by the solid line in FIG. 23A, and the reference exposure results are output as samples. Based on the reference exposure result outputted from the sample, a micromirror to be used in the main exposure can be designated.
For example, a micromirror other than the micromirror corresponding to the light spot group indicated by hatching in FIG. 23B is designated as actually used in the main exposure among the micromirrors in the first to 128th rows. Can be done. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used in the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
By designating the micromirror to be used at the time of the main exposure in this way, a state close to an ideal double exposure can be realized in the main exposure using the entire micromirror.

FIG. 24 uses a plurality of exposure heads, and two adjacent exposure heads (for example, exposure heads 30 ₁₂ and 30 ₂₁ ) adjacent to each other in the X-axis direction are adjacent to each other corresponding to 1 / N rows of the total number of light spots. It is explanatory drawing which showed an example of the form which performs reference exposure using only the micromirror group which comprises a line.
In this example, it is assumed that double exposure is performed during the main exposure, and therefore N = 2. First, reference exposure is performed using only the micromirrors corresponding to the light spots in the first to 128th (= 256/2) rows indicated by solid lines in FIG. 24, and the reference exposure results are output as samples. . Based on the reference exposure result outputted from the sample, it is possible to realize the main exposure in which the variation in resolution and the density unevenness in the region other than the joint region between the heads formed on the exposed surface by the two exposure heads are minimized. In addition, it is possible to designate a micromirror to be used during the main exposure.
For example, micromirrors other than the micromirrors corresponding to the light spot arrays in the region 90 shown by hatching in FIG. 24 and the region 92 shown by shading are included in the micromirrors in the first to 128th rows. Designated as actually used at the time of exposure. For the micromirrors in the 129th to 256th rows, reference exposure may be separately performed in the same manner, and the micromirrors used for the main exposure may be designated, or the micromirrors in the first to 128th rows may be designated. The same pattern as that for the mirror may be applied.
In this way, by specifying the micromirror to be used during the main exposure, a state close to ideal double exposure is realized in an area other than the inter-head connecting area formed on the exposed surface by two exposure heads. it can.

  In the above embodiments (1) to (3) and the modified examples, the case where the main exposure is the double exposure has been described. However, the present invention is not limited to this, and any multiple exposure more than the double exposure may be used. . In particular, by setting the exposure to about 3 to 7 exposures, high resolution can be secured, and exposure with reduced variations in resolution and density unevenness can be realized.

  Further, in the exposure apparatus according to the embodiment and the modified example, the dimension of the predetermined part of the two-dimensional pattern represented by the image data is matched with the dimension of the corresponding part that can be realized by the selected use pixel. A mechanism for converting image data is preferably provided. By converting the image data in this way, a high-definition pattern according to a desired two-dimensional pattern can be formed on the exposed surface.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, an etching process, a plating process, a hardening process process, etc. are mentioned. These may be used alone or in combination of two or more.
The development step is a step of forming a pattern by exposing the photosensitive layer in the pattern forming material by the exposure step, curing the exposed region of the photosensitive layer, and then developing by removing an uncured region. is there.

-Development process-
The developing step can be preferably performed by, for example, developing means.
The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, means for spraying the developer, means for applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, an alkaline solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline liquid include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

-Etching process-
The etching step can be performed by a method appropriately selected from known etching methods.
There is no restriction | limiting in particular as an etching liquid used for the said etching process, According to the objective, it can select suitably, For example, when the said metal layer is formed with copper, a cupric chloride solution, chloride. A ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, and the like can be given. Among these, a ferric chloride solution is preferable from the viewpoint of an etching factor.
An etching pattern can be formed on the surface of the substrate by removing the pattern after performing the etching process in the etching step.
There is no restriction | limiting in particular as said etching pattern, According to the objective, it can select suitably, For example, a wiring pattern etc. are mentioned suitably.

-Plating process-
The plating step can be performed by an appropriately selected method selected from known plating processes.
Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.
An etching pattern can be formed on the surface of the substrate by removing the pattern after plating by the plating step and further removing unnecessary portions by etching or the like as necessary.

-Curing process-
The said hardening process process is a process of performing the hardening process with respect to the formed pattern after the said image development process was performed with respect to the said photosensitive layer which consists of the said photosensitive composition for soldering resists.

  There is no restriction | limiting in particular as said hardening process, According to the objective, it can select suitably, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the photosensitive laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, According to the objective, it can select suitably, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the photosensitive laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

[Method of manufacturing printed wiring board]
The said pattern formation method of this invention can be used suitably for manufacture of a printed wiring board, especially the manufacture of a printed wiring board which has hole parts, such as a through hole or a via hole. Hereinafter, an example of the manufacturing method of the printed wiring board using the pattern formation method of this invention is demonstrated.

  As a method for producing a printed wiring board having a hole portion such as a through hole or a via hole, (1) the pattern forming material is formed on a printed wiring board forming substrate having a hole portion as the substrate, and the photosensitive layer is the substrate. (2) The photosensitive layer is irradiated with light from a side opposite to the base of the photosensitive laminate to cure the photosensitive layer, 3) removing the support in the pattern forming material from the photosensitive laminate, and (4) developing the photosensitive layer in the photosensitive laminate to remove the uncured portion in the photosensitive laminate. A pattern can be formed.

  The removal of the support in (3) may be performed between (1) and (2) instead of between (2) and (4).

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate using the formed pattern (for example, a known subtractive method or additive method (for example, a semi-additive method) And the full additive method)). Among these, in order to form a printed wiring board by industrially advantageous tenting, the subtractive method is preferable. After the treatment, the cured resin remaining on the printed wiring board forming substrate is peeled off. In the case of the semi-additive method, a desired printed wiring board can be manufactured by further etching the copper thin film portion after peeling. it can. A multilayer printed wiring board can also be manufactured in the same manner as the printed wiring board manufacturing method.

  Next, the manufacturing method of the printed wiring board which has a through hole using the said pattern formation material is further demonstrated.

  First, a printed wiring board forming substrate having through holes and having a surface covered with a metal plating layer is prepared. As the printed wiring board forming substrate, for example, a copper-clad laminate substrate and a substrate in which a copper plating layer is formed on an insulating substrate such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer A substrate (laminated substrate) can be used.

Next, when a protective film is provided on the pattern forming material, the protective film is peeled off so that the photosensitive layer in the pattern forming material is in contact with the surface of the printed wiring board forming substrate. Is used for pressure bonding (lamination process). Thereby, the photosensitive laminated body which has the said board | substrate for printed wiring board formation and the said photosensitive laminated body in this order is obtained.
There is no restriction | limiting in particular as lamination | stacking temperature of the said pattern formation material, For example, room temperature (15-30 degreeC) or under heating (30-180 degreeC) is mentioned, Among these, under heating (60-140 degreeC) Is preferred.
There is no restriction | limiting in particular as roll pressure of the said crimping | compression-bonding roll, For example, 0.1-1 Mpa is preferable.
There is no restriction | limiting in particular as the speed | rate of the said crimping | compression-bonding, and 1-3 m / min is preferable. The printed wiring board forming substrate may be preheated or laminated under reduced pressure.

  The photosensitive laminate may be formed by laminating the pattern forming material on the printed wiring board forming substrate, and forming the printed wiring board with a photosensitive composition solution for manufacturing the pattern forming material. The photosensitive layer and the support may be laminated on the printed wiring board forming substrate by applying directly to the surface of the printing substrate and drying.

  Next, light is irradiated from the surface of the photosensitive laminate opposite to the substrate to cure the photosensitive layer. At this time, exposure may be performed after peeling off the support as necessary (for example, when the light transmittance of the support is insufficient).

  At this time, if the support is not yet peeled, the support is peeled from the photosensitive laminate (peeling step).

  Next, the uncured region of the photosensitive layer on the printed wiring board forming substrate is dissolved and removed with an appropriate developer to form a pattern of the cured layer for forming the wiring pattern and the cured layer for protecting the metal layer of the through hole. And a metal layer is exposed on the surface of the printed wiring board forming substrate (developing step).

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. The development may be a wet development method as described above or a dry development method.

  Next, the metal layer exposed on the surface of the printed wiring board forming substrate is dissolved and removed with an etching solution (etching step). Since the opening of the through hole is covered with a cured resin composition (tent film), the metal plating of the through hole is predetermined without etching liquid entering the through hole and corroding the metal plating in the through hole. It will remain in the shape. Thus, a wiring pattern is formed on the printed wiring board forming substrate.

  There is no restriction | limiting in particular as said etching liquid, According to the objective, it can select suitably, For example, when the said metal layer is formed with copper, a cupric chloride solution, a ferric chloride solution, Examples include alkaline etching solutions and hydrogen peroxide-based etching solutions. Among these, ferric chloride solutions are preferable from the viewpoint of etching factors.

Next, it removes from the said board | substrate for printed wiring board formation by making the said hardened layer into a peeling piece with strong alkaline aqueous solution etc. (hardened | cured material removal process).
There is no restriction | limiting in particular as a base component in the said strong alkali aqueous solution, For example, sodium hydroxide, potassium hydroxide, etc. are mentioned.
As pH of the said strong alkali aqueous solution, about 12-14 are preferable, for example, and about 13-14 are more preferable.
There is no restriction | limiting in particular as said strong alkali aqueous solution, For example, 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution etc. are mentioned.

  The printed wiring board may be a multilayer printed wiring board. The pattern forming material may be used not only for the above etching process but also for a plating process. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high flow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating. And gold plating such as soft gold plating.

When the substrate is a printed wiring board such as a multilayer wiring board, a solder resist photosensitive layer made of the photosensitive composition is formed on the printed wiring board, and soldering is performed as follows. be able to.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

  Preparation of alkali-soluble photocrosslinkable resins (P1) to (P2) (Synthesis Examples 1 and 2), pigments and inorganic filler dispersions (Synthesis Example 13) as binders contained in the photosensitive composition for solder resists is as follows. It was synthesized as follows.

(Synthesis Example 1) Synthesis of Alkali-Soluble Photocrosslinkable Resin (P1) cresol novolak type epoxy resin Epicron N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent = 220) 220 parts by mass was stirred and reflux condenser In a four-necked flask, and 214 parts by weight of carbitol acetate was added and dissolved by heating. Next, 0.1 part by mass of hydroquinone as a polymerization inhibitor and 2.0 parts by mass of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., 72 parts by mass of acrylic acid was added dropwise, and reacted for 16 hours. The reaction product is cooled to 80 to 90 ° C., 106 parts by mass of tetrahydrophthalic anhydride is added and reacted for 8 hours. After cooling, 52 parts by mass of carbitol acetate is added, and the solid content concentration is 60% by mass. An alkali-soluble photocrosslinkable resin (P1) was obtained. The acid value of P1 of solids 100 mg KOH / g, Bromine Number 39gBr ₂ / 100g, the weight average molecular weight was 4,020.

(Synthesis Example 2)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 145 parts by mass of methoxypropyl acetate was taken, stirred while replacing with nitrogen, and heated to 120 ° C. Next, t-butyl hydroperoxide (Nippon Yushi Co., Ltd.) was added to a monomer mixture consisting of 10.4 parts by mass of styrene, 71 parts by mass of glycidyl methacrylate and 82 parts by mass of dicyclopentenyl acrylate (FA-511A manufactured by Hitachi Chemical Co., Ltd.). 7.6 parts by mass of Perbutyl O) was added. This mixed solution was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours. Next, the inside of the flask was replaced with air, 0.9 parts by mass of trisdimethylaminomethylphenol and 0.145 parts by mass of hydroquinone were added to 34.2 parts by mass of acrylic acid, and the flask was heated at 120 ° C. for 6 hours. The reaction was continued and the reaction was terminated when the solid content acid value was 0.8. Further, 60.8 parts by mass of tetrahydrophthalic anhydride (84.2 mol% of the generated hydroxyl group), 0.8 parts by mass of triethylamine Was added and reacted at 120 ° C. for 3.5 hours, and diluted with methoxypropyl acetate to a solid content concentration of 60% by mass to obtain an alkali-soluble photocrosslinkable polymer (P2). Solids acid value of P2 is 84 mgKOH / g, the bromine number is 29gBr ₂ / 100g, the weight average molecular weight was 12,000.

(Synthesis Example 3)
Pigment Blue 15: 3 is 0.80 part by mass, Pigment Yellow 180 is 0.7 part by mass, and a mass ratio of 1: 1 mixture of P1 and P2 is 15 parts by mass of a 60% by mass methoxypropyl acetate solution. Dispersion was performed using a mill type disperser filled with zirconia beads to obtain a green pigment dispersion.
Subsequently, 18 parts by mass of barium sulfate as an inorganic filler was mixed and stirred in the green pigment dispersion to obtain 81.4 parts by mass of a co-dispersion with a green pigment (solid content concentration 35% by mass).

Example 1
<Preparation of photosensitive composition coating solution for solder resist>
The following components (see Table 1) were mixed to prepare a photosensitive composition coating solution for solder resist.
――――――――――――――――――――――――――――――――――――――――
60% by mass solution of alkali-soluble photocrosslinkable oligomer (P1) synthesized in Synthesis Example 1 ... 31.8 parts by mass 60% by mass solution of alkali-soluble photocrosslinkable polymer (P2) synthesized in Synthesis Example 2 .8 mass parts bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 1004) ... 14.3 mass parts dipentaerythritol hexaacrylate (Nippon Kayaku DPHA) ... 18.9 mass parts N -N-butyl-2-chloroacridone (acridine derivative) ... 2.2 parts by mass Illustrative compound (III-1) (onium compound, radical generator) ... 6.6 parts by mass Pigment dispersion (synthesis) Example 3) 81.4 parts by mass Dicyandiamide 0.7 parts by mass Imidazole derivative (2,4-diamino-6- {2'-methylimidazole- (1 ')}-Ethyl-s-triazine isocyanuric acid adduct) ... 0.53 parts by mass Surfactant (manufactured by Dainippon Ink Co., Ltd., 30 wt% methyl ethyl ketone solution of F780F) ... 0.07 parts by mass Hydroquinone monomethyl ether ・ ・ ・ 0.07 parts by mass ―――――――――――――――――――――――――――――――――――――――― -

-Production of photosensitive solder resist film and solder resist-
The solder resist photosensitive composition solution was applied onto a 25 μm thick polyethylene terephthalate film (Toray Industries, Lumirror 16QS52) support with a bar coater to a thickness of 30 μm after drying, and 80 ° C. for 30 minutes. It dried in the hot air circulation type dryer, the photosensitive layer was formed, and the photosensitive soldering resist film as a pattern formation material was produced. The obtained photosensitive solder resist film was laminated on a copper clad laminate with a laminator. As shown in FIG. 35, a copper clad laminate 3, a photosensitive layer 2, and the polyethylene terephthalate film (support) 1 were The said photosensitive laminated body laminated | stacked in this order was prepared. The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.
Subsequently, it exposed at 40 mJ / cm < ² > using the blue-violet laser irradiation apparatus which has a predetermined pattern. Thereafter, spray development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 60 seconds at a pressure of 1.8 MPa (1.8 kgf / cm ² ), and the unexposed area was dissolved and developed. Using the obtained images, the sensitivity, resolution, storage stability, and line width of the resist pattern were evaluated by the following methods. The results are shown in Table 2.
Next, a solder resist pattern as a permanent pattern similarly formed on the comb-shaped electrode substrate was heated at 150 ° C. for 1 hour to prepare a test plate. The test plate was evaluated for pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance. The results are shown in Table 3.

<Minimum development time>
The polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. photosensitive layer on the copper-clad laminate to measure the time required before being dissolved and removed from the starting spray, which was the shortest development time (t _o).
As a result, the shortest development time (t _o ) was 20 seconds.

<Sensitivity>
With respect to the photosensitive layer of the pattern forming material in the laminate, from a polyethylene terephthalate film (support) side, using a pattern forming apparatus having a 405 nm laser light source as the light irradiation means, 0.1 mJ / cm ² to 2 Exposure was performed by irradiating with light having different light energy amounts up to 100 mJ / cm ² at ^½ times intervals to cure a part of the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) is sprayed on the entire surface of the photosensitive layer on the copper clad laminate. Spraying was performed at a pressure of 0.15 MPa for twice the shortest development time, and the uncured region was dissolved and removed, and the thickness of the portion other than the portion removed by development (cured region) was measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was 30 μm was defined as the minimum amount of light energy (sensitivity) necessary for curing the photosensitive layer. The pattern forming apparatus includes a light modulating unit made of the DMD and includes the pattern forming material.

<Resolution>
The laminate is allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes, and from the polyethylene terephthalate film (support) of the laminate using the pattern forming apparatus, line / space = 1/1. Then, each line width was exposed in 1 μm increments from 5 μm to 20 μm in line width, and each line width was exposed in 5 μm increments from 20 μm to 50 μm in line width. The exposure amount at this time is the minimum amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by the sensitivity measurement. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the laminate. An aqueous solution of sodium carbonate (30 ° C., 1% by mass) as the developer is sprayed over the entire surface of the photosensitive layer on the copper-clad laminate at a spray pressure of 0.15 MPa for twice the shortest development time to obtain an uncured region Was dissolved and removed. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. did. The smaller the numerical value, the better the resolution.

<Storage stability (change in developability)>
The obtained photosensitive solder resist film (pattern forming material) is placed in a light-proof moisture-proof bag (BF3X, manufactured by Tokai Aluminum Foil Co., Ltd.) having a laminated structure of black vinyl and aluminum foil, and 3 in a dry oven at 40 ° C. Stored for days. Then removed the film, it performs the shortest development time test described above after laminated on a substrate, and measured the shortest developing time (t _3).
The shortest development time (t ₃ ) was compared with the shortest development time (t ₀ ) on the day of preparation of the above-described photosensitive solder resist film by the value of the t ₃ / t ₀ ratio.
Based on this value, storage stability was evaluated as follows.
○: 1.0 to 1.3
Δ: 1.3-1.8
X: 1.8 or more

<Pencil hardness>
The test plate on which the solder resist pattern (permanent pattern) had been formed was subjected to gold plating according to a conventional method and then subjected to water-soluble flux treatment. Subsequently, it was immersed three times in a solder bath set at 260 ° C. for 5 seconds, and the flux was removed by washing with water. And the pencil hardness was measured about the permanent pattern after this flux removal based on JISK-5400.
As a result, the pencil hardness was 5H.

<Adhesion>
Based on JIS K-5400, 100 pieces of 1 mm × 1 mm crumbs were prepared on the cured test piece, and a peel test was performed using a cellophane tape. The state of peeling of the goblet was observed and evaluated according to the following criteria.
○: No peeling at 90/100 or more Δ: No peeling at 50/100 or more to less than 90/100 ×: No peeling at 0/100 to less than 50/100

<Solvent resistance>
The cured test piece was immersed in isopropyl alcohol at room temperature for 30 minutes, and after confirming that there was no abnormality in appearance, a peel test was performed using a cellophane tape. The appearance of the coating film at that time was observed and evaluated according to the following criteria.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

<Acid resistance>
After curing, the test piece was immersed in a 10% by mass hydrochloric acid aqueous solution at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape. The appearance of the coating film at that time was observed and evaluated according to the following criteria.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

<Alkali resistance>
The test piece after curing was immersed in a 5% by mass aqueous sodium hydroxide solution at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape. The appearance of the coating film at that time was observed and evaluated according to the following criteria.
○: There is no abnormality in the appearance of the coating film and there is no peeling ×: There is an abnormality in the appearance of the coating film or peeling

<Solder heat resistance>
A water-soluble flux was applied to the test piece and immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following criteria.
○: There is no abnormality (peeling or swelling) in the appearance of the coating film, and there is no dent due to solder. △: An abnormality (peeling or swelling) occurs in rare cases. ×: There is an abnormality (peeling or swelling) in the coating film appearance. There is a dent by solder

<Insulation resistance>
Using IPC-B-25 comb-shaped test pattern B, wearing a photomask for pattern B, the entire surface was exposed at 40 mJ / cm ² by the blue-violet laser irradiation apparatus, and 1% by mass of carbonic acid at 30 ° C. for 60 seconds. Development, washing with water and drying with an aqueous sodium solution were carried out, and a test substrate was prepared by post-heating treatment at 150 ° C. for 1 hour. About the obtained test board, the insulation resistance in 25 degreeC and 50% RH was measured according to the test method of IPC-SM-840B, and the following criteria evaluated.
[Criteria]
○: Insulation resistance value is 5 × 10 ⁸ Ω or more
×: Insulation resistance value is less than 5 × 10 ⁸ Ω

<Gold resistance>
The test substrate on which the solder resist pattern was formed was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) at 30 ° C. for 3 minutes and then washed with water.
Next, the test substrate was immersed in a 14.4% by volume aqueous ammonium persulfate solution at room temperature for 3 minutes and then washed with water. Further, the test substrate was immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water.
Next, this substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 volume% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate Ni After -8, it was immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water.
Next, the test substrate is immersed in a gold plating solution at 95 ° C. (Meltex, aqueous solution of 15% by volume of Aurolectroles UP and 3% by volume of potassium cyanide, pH 6) for 10 minutes, subjected to electroless gold plating, and then washed with water. Further, it was immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. The obtained electroless gold plating evaluation board was observed and evaluated according to the following criteria.
○: No abnormality at all ×: Bad plating adhesion or dent due to plating

<Heat shock resistance>
As a reliability test item, a crack was evaluated according to the following criteria by a temperature cycle test (TCT).
Here, TCT uses a gas-phase cooling / heating tester (EHS-212MD, manufactured by Espec Corp.), and the test plate is left in the gas phase at −55 ° C. and 125 ° C. for 30 minutes, and this is performed for one cycle. As above, it was performed under the condition of 1,000 cycles.
○: No crack occurred △: Shallow crack occurred ×: Deep crack occurred

(Examples 2 to 15 and Comparative Examples 1 to 6)
In Example 1, except that at least one of the acridine derivative, the radical generator, the hydrogen donor component, and the content was changed as shown in Table 1, each of the examples was changed. A test plate in which a solder resist pattern was heated was formed on the photosensitive solder resist film, the photosensitive laminate, and the substrate, and the sensitivity, resolution, and storage stability of the photosensitive solder resist film were evaluated. The results are shown in Table 2.
The test plate was evaluated for pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance. The results are shown in Table 3.
In Comparative Example 1, an image could not be obtained and could not be evaluated.

(Example 16)
In Example 9, except that 0.11 part by mass of N-phenylglycine was added as a hydrogen donor compound, a photosensitive solder resist film, a photosensitive laminate, and a solder on the substrate were used in the same manner as in Example 9. A test plate heated with a resist pattern was formed, and the sensitivity, resolution, and storage stability of the photosensitive solder resist film were evaluated. The results are shown in Table 2.
The test plate was evaluated for pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance. The results are shown in Table 3.

Abbreviations of each compound in Table 1 correspond as follows.
SD-1: 2-chloro-N- (n-butyl) acridone SD-2: N-methylacridone SD-3: N-ethylacridone SD-4: acridone AP-1: 2,2′-bis ( o-Chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole
AP-2: 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butan-1-one
H-1: N-phenylglycine In Table 1, “content (parts by mass)” means the content in the total solid content of the photosensitive layer.

From the results of Tables 2 and 3, in the photosensitive solder resist films of Examples 1 to 16, the storage stability is high, and the photosensitive layer made of the photosensitive composition of the present invention is highly sensitive to the blue ultraviolet laser. In addition, excellent light stability and thermal stability under yellow safety light, pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, gold plating resistance, and thermal shock resistance It was found that a good pattern can be formed.

(Example 17)
-Production of pattern forming material-
A photosensitive film solution for dry film resist having the following composition was applied on a 16 μm thick polyethylene terephthalate film (Toray Co., Ltd., 16QS52) as a support and dried, and a 15 μm thick photosensitive layer was formed on the support. To form a pattern forming material.

[Composition of photosensitive composition solution]
Phenothiazine: 0.0122 parts by mass Methacrylic acid / methyl methacrylate / styrene copolymer (copolymer composition (mass ratio): 29/19/52, mass average molecular weight: 60,000, acid value 189, Tg: 131 ° C) ... 50.2 parts by mass Polymerizable monomer represented by the following structural formula (36) ... 15.7 parts by mass 1/2 mole ratio adduct of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate ... 14.1 parts by mass dodecapropylene glycol diacrylate (manufactured by Toagosei Chemical Co., Ltd., M-270) ... 1.57 parts by mass tricosaethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., 23G) ... 10.5 10 parts by mass of 10-n-butyl-2-chloroacridone (acridine derivative) ... 0.36 parts by mass of exemplified compound (III-1) (Onium compound, radical generator) ... 5.1 parts by mass Malachite green oxalate ... 0.068 parts by mass Leuco Crystal Violet ... 0.41 parts by mass methyl ethyl ketone ... 160 parts by mass 1-methoxy 2-Propanol ... 80 parts by mass
Fluorosurfactant (F780F, manufactured by Dainippon Ink, Inc.) 0.087 parts by mass

However, m + n represents 10 in Structural Formula (36).

On the photosensitive layer of the pattern forming material, a 12 μm-thick polypropylene film (manufactured by Oji Paper Co., Ltd., Alphan E-501) was laminated as the protective film to obtain a dry film material for pattern formation.
Next, a laminator (MODEL8B-720-PH) is used as the substrate while peeling the protective film of the pattern forming material on the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) polished, washed and dried. , Manufactured by Taisei Laminator Co., Ltd.) to prepare the photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 0.3 MPa, and a laminating speed of 1 m / min.

  The sensitivity and resolution of the photosensitive layer were evaluated in the same manner as in Example 1, and the line width of the resist pattern was evaluated by the following method. Further, the storage stability of the pattern forming material was evaluated by the following method. The results are shown in Table 5.

<Storage stability (sensitivity change)>
The pattern forming material is put into a light-shielding moisture-proof bag (BF3X, manufactured by Tokai Aluminum Foil Co., Ltd.) having a laminated structure of black vinyl and aluminum foil, and left to stand in an environment of a temperature of 50 ° C. for 3 days. The sensitivity (S ₃ ) is measured by the same method as above, and the sensitivity fluctuation rate is calculated by the following formula from the ratio with the initial sensitivity (S ₀ ). Based on this, the storage stability was evaluated.
〔formula〕
Sensitivity fluctuation rate = (S ₀ −S ₃ ) / S ₀ × 100 (%)
〔Evaluation criteria〕
○: Sensitivity fluctuation rate less than ± 10% ×: Sensitivity fluctuation rate ± 10% or more

<Line width of resist pattern>
(1) Measurement of resist line width The laminate was allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate (support) of the laminate, the pattern forming apparatus is used to irradiate 20 patterns each having a hole with a width of 50 μm and a length of 300 μm. And a part of the photosensitive layer was cured. The exposure amount at this time is the minimum amount of light energy necessary for curing the photosensitive layer of the pattern forming material obtained by the sensitivity measurement.
This was developed as described above to dissolve and remove uncured regions. The obtained pattern was observed with an optical microscope, the width of the bottom of the formed pattern was measured, the average value of the widths was determined, and this was used as the line width of the resist pattern.

(2) Measurement of fluctuation amount of line width of resist pattern With a safe light (yellow fluorescent lamp) (manufactured by Hitachi, FLR40S-Y / MB), illuminance of 500 lx (measured by Minolta, T-1M) About the laminated body before irradiating light for 6 hours, and the laminated body after the said irradiation, the line width of a resist pattern is measured by the measuring method of (1), and the absolute value of the difference is the line width of the resist pattern. Measured as variation. The results are shown in Table 5.

(Examples 18 to 21 and Comparative Examples 7 and 8)
In Example 8, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 8, except that at least one of the compounds and contents of the acridine derivative and the radical generator was changed as shown in Table 4. Then, the sensitivity of the photosensitive layer, the resolution, and the line width variation amount of the resist pattern were evaluated, and the storage stability of the pattern forming material was evaluated. The results are shown in Table 5.

(Example 22)
In Example 19, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 19 except that 1.0 part by mass of N-phenylglycine was added as a hydrogen donor compound. The resolution and the line width variation of the resist pattern were evaluated, and the storage stability of the pattern forming material was evaluated. The results are shown in Table 5.

(Example 23)
In Example 17, a pattern forming material and a photosensitive laminate were produced in the same manner as in Example 17 except that exposure was performed by the following method using a pattern forming apparatus described below. Then, the resolution and the line width of the resist pattern were evaluated, and the storage stability of the pattern forming material was evaluated. The results are shown in Table 5.

<Pattern forming apparatus and exposure method>
The combined laser light source shown in FIGS. 8 to 9 and 25 to 29 as the light irradiating means, and 1024 micromirrors 58 arranged in the main scanning direction schematically shown in FIG. 6 as the light modulating means. A DMD 36 controlled to drive only 1024 × 256 rows among 768 pairs of mirror rows arranged in the sub-scanning direction, and an optical system that focuses the light shown in FIG. 5 on the pattern forming material. The pattern forming apparatus 10 provided with the exposure head 30 having the same was used.

As the set inclination angle of each exposure head 30, that is, each DMD 36, an angle slightly larger than the angle θ _{ideal at} which double exposure is performed using a usable 1024 column × 256 row micromirror 58 was adopted. This angle θ _ideal is equal to the number N of N double exposures, the number s of usable micromirrors 58 in the column direction, the interval p of usable micromirrors 58 in the column direction, and the microscopic exposure head 30 in a tilted state. For the pitch δ of the scanning line formed by the mirror,
spsinθ _ideal ≧ Nδ (Formula 1)
Given by. As described above, the DMD 36 according to the present embodiment includes a large number of micromirrors 58 having equal vertical and horizontal arrangement intervals arranged in a rectangular lattice shape.
pcosθ _ideal = δ (Formula 2)
And the above equation 1 is
stanθ _ideal = N (Formula 3)
Since s = 256 and N = 2, the angle θ _ideal is about 0.45 degrees. Therefore, for example, 0.50 degrees is adopted as the set inclination angle θ.

First, the state of the exposure pattern on the exposed surface was examined in order to correct the variation in resolution and uneven exposure in double exposure. The results are shown in FIG. In FIG. 18, the light spot group from the micromirror 58 that can be used by the DMD 36 of the exposure heads 30 ₁₂ and 30 ₂₁ projected onto the exposed surface of the pattern forming material 12 with the stage 14 being stationary. Showed the pattern. The state of the exposure pattern formed on the exposed surface when the stage 14 is moved and the continuous exposure is performed with the light spot group pattern as shown in the upper part appearing in the lower part. Are shown for exposure areas 32 ₁₂ and 32 ₂₁ . In FIG. 18, for convenience of explanation, every other exposure pattern of the micromirrors 58 that can be used is divided into an exposure pattern based on the pixel column group A and an exposure pattern based on the pixel column group B. The actual exposure pattern on the exposed surface is a superposition of these two exposure patterns.

As shown in FIG. 18, as a result of the deviation of the relative position between the exposure heads 30 ₁₂ and 30 ₂₁ from the ideal state, both the exposure pattern by the pixel column group A and the exposure pattern by the pixel column group B are both. Thus, it can be seen that, in the exposure areas overlapping on the coordinate axes orthogonal to the scanning direction of the exposure head in the exposure areas 32 ₁₂ and 32 ₂₁ , an overexposed area is generated as compared with the ideal double exposure state.

The use of a set of slits 28 and a photodetector as a light spot position detection means, the position of the point P of the exposure head _{30 12} For the exposure area _{32 12} (1,1) and P (256,1), the exposure head For 30 ₂₁ , the positions of the light spots P (1,1024) and P (256, 1024) in the exposure area 32 ₂₁ are detected, and the angle formed by the inclination angle of the straight line connecting them and the scanning direction of the exposure head is determined. It was measured.

Using the actual inclination angle θ ′, the following equation 4
ttanθ ′ = N (Formula 4)
The natural number T closest to the value t satisfying the relationship is derived for each of the exposure heads 30 ₁₂ and 30 ₂₁ . T = 254 for the exposure head _{30 12,} the exposure head _{30 21} T = 255 was derived respectively. As a result, the micromirrors constituting the portions 78 and 80 covered with diagonal lines in FIG. 19 were identified as micromirrors that are not used during the main exposure.

Thereafter, the micromirrors corresponding to the light spots other than the light spots constituting the regions 78 and 80 covered with the oblique lines in FIG. 19 were similarly covered with the shaded areas 82 and the shaded areas in FIG. Micromirrors corresponding to the light spots constituting the region 84 were identified and added as micromirrors that are not used during the main exposure.
With respect to the micromirrors that are specified not to be used at the time of exposure, a signal for setting the angle of the always-off state is sent by the pixel element control means, and these micromirrors are substantially exposed. It was controlled not to be involved.
As a result, in each of the exposure areas 32 ₁₂ and 32 ₂₁ , an ideal double exposure is performed in each area other than the inter-head connection area, which is an overlapping exposure area on the exposed surface formed by the plurality of exposure heads. Thus, the total area of the overexposed region and the underexposed region can be minimized.

In addition, the abbreviation and content of each compound in Table 4 represent the same meaning as in Table 1.

From the results of Table 5, the pattern forming material formed by forming the photosensitive layer using the photosensitive composition of the invention of Examples 17 to 23 has high storage stability, and the photosensitive layer made of the photosensitive composition of the invention. Is highly sensitive to blue-ultraviolet lasers, and is excellent in light stability and thermal stability under a yellow safety light, and it is found that a pattern can be efficiently formed with high definition. Furthermore, it was found that the pattern formed by the exposure method of Example 23 had a very small line width variation and high definition.

The photosensitive composition of the present invention, the pattern forming material having a photosensitive layer formed from the photosensitive composition, and the photosensitive laminate are highly sensitive to a blue ultraviolet laser, and under a yellow safety light. Excellent light stability and thermal stability, extremely high storage stability, and high-definition and efficient pattern formation. Various patterns, permanent patterns such as wiring patterns, color filters, etc. It can be suitably used for the production of liquid crystal structural members such as pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., and can be particularly suitably used for the formation of high-definition wiring patterns.
Since the pattern forming apparatus and pattern forming method of the present invention include the photosensitive laminate of the present invention, formation of various patterns, formation of permanent patterns such as wiring patterns, color filters, pillar materials, rib materials, spacers It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of high-definition wiring patterns.

FIG. 1 is a perspective view showing an appearance of an example of a pattern forming apparatus. FIG. 2 is a perspective view showing an example of the configuration of the scanner of the pattern forming apparatus. FIG. 3A is a plan view showing an exposed region formed on the exposed surface of the photosensitive layer. FIG. 3B is a plan view showing an arrangement of exposure areas by each exposure head. FIG. 4 is a perspective view showing an example of a schematic configuration of the exposure head. FIG. 5A is a top view showing an example of a detailed configuration of the exposure head. FIG. 5B is a side view showing an example of a detailed configuration of the exposure head. FIG. 6 is a partially enlarged view showing an example of the DMD of the pattern forming apparatus of FIG. FIG. 7A is a perspective view for explaining the operation of the DMD. FIG. 7B is a perspective view for explaining the operation of the DMD. FIG. 8 is a perspective view showing an example of the configuration of the fiber array light source. FIG. 9 is a front view showing an example of the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 10 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is an exposure head mounting angle error and pattern distortion. FIG. 11 is a top view showing a positional relationship between an exposure area by one DMD and a corresponding slit. FIG. 12 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 13 is an explanatory diagram showing a state in which unevenness generated in a pattern on an exposed surface is improved as a result of using only selected micromirrors for exposure. FIG. 14 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift between adjacent exposure heads. FIG. 15 is a top view showing the positional relationship between the exposure areas by two adjacent exposure heads and the corresponding slits. FIG. 16 is a top view for explaining a method of measuring the position of the light spot on the exposed surface using a slit. FIG. 17 is an explanatory diagram showing a state in which only the used pixels selected in the example of FIG. 14 are actually moved and the unevenness in the pattern on the exposed surface is improved. FIG. 18 is an explanatory diagram showing an example of unevenness that occurs in the pattern on the exposed surface when there is a relative position shift and a mounting angle error between adjacent exposure heads. FIG. 19 is an explanatory diagram showing exposure using only the used pixel portion selected in the example of FIG. FIG. 20A is an explanatory diagram showing an example of magnification distortion. FIG. 20B is an explanatory diagram showing an example of beam diameter distortion. FIG. 21A is an explanatory view showing a first example of reference exposure using a single exposure head. FIG. 21B is an explanatory diagram showing a first example of reference exposure using a single exposure head. FIG. 22 is an explanatory diagram showing a first example of reference exposure using a plurality of exposure heads. FIG. 23A is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 23B is an explanatory diagram showing a second example of reference exposure using a single exposure head. FIG. 24 is an explanatory view showing a second example of reference exposure using a plurality of exposure heads. FIG. 25 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 26 is an example of a plan view showing the configuration of the combined laser light source. FIG. 27 is an example of a plan view showing the configuration of the laser module. FIG. 28 is an example of a side view showing the configuration of the laser module shown in FIG. FIG. 29 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 30 is an example of a perspective view showing a configuration of a laser array. FIG. 31A is an example of a perspective view showing a configuration of a multi-cavity laser. FIG. 31B is an example of a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. 31A are arranged in an array. FIG. 32 is an example of a plan view showing another configuration of the combined laser light source. FIG. 33 is an example of a plan view showing another configuration of the combined laser light source. FIG. 34A is an example of a plan view showing another configuration of the combined laser light source. FIG. 34B is an example of a cross-sectional view along the optical axis of FIG. 34A. FIG. 35 is an explanatory diagram showing a layer structure of a photosensitive solder resist film.

Explanation of symbols

1 Support 2, 12 Photosensitive layer (photosensitive material)
3 Copper-clad laminates B1 to B7 Laser beams L1 to L7 Collimator lenses LD1 to LD7 GaN-based semiconductor laser 10 Pattern forming device 14 Moving stage 18 Installation table 20 Guide 22 Gate 24 Scanner 26 Sensor 28 Slit 30 Exposure head 32 Exposure area 36 Digital・ Micromirror device (DMD)
38 Fiber array light source 58 Micro mirror (picture element)
60 laser module 62 multimode optical fiber 64 optical fiber 66 laser emitting section 110 heat block 111 multicavity laser 113 rod lens 114 lens array 140 laser array 200 condenser lens

Claims (19)

A photosensitivity comprising at least a binder, a polymerizable compound, and a photopolymerization initiating compound, wherein the photopolymerization initiating compound comprises an acridine derivative represented by the following general formula (I) and an onium compound: Composition.
In the general formula (I), A is an oxygen atom, represents one of a sulfur atom, and ^{NR 10, R 1, R 2} , R 3, R 4, R 5, R 6, R 7, R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent, and groups adjacent to each other may be bonded to form a ring. The monovalent substituent may further have a substituent. The photosensitive composition according to claim 1, wherein the acridine derivative is an acridone compound represented by the following general formula (II).
However, in said general formula (II), R < ¹ >, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R <^7> , and R <^8> are each independently a hydrogen atom and a monovalent substituent. R ⁹ represents an alkyl group. Adjacent groups may combine to form a ring. The monovalent substituent may further have a substituent.   The photosensitive composition according to claim 1, wherein the onium compound is at least one selected from an iodonium compound, a sulfonium compound, and a pyridinium compound. The photosensitive composition of Claim 3 by which a pyridinium compound is represented by the following general formula (a).
However, in said general formula (a), R <^15> , R <^16> , R <^17> , R <^18> . R ¹⁹ and R ²⁰ represent an organic group which may be the same or different from each other, and at least one of these represents an organic group represented by the following general formula (a-1). X ^m− represents an m-valent anion, and m represents an integer of 1 to 6.
However, in General Formula (a-1), R ²¹ , R ²² , and R ²³ represent an organic group that may be the same as or different from each other, and L is a divalent that may contain a hetero atom. Represents a linking group.   The photosensitive composition in any one of Claim 1 to 4 containing a hydrogen donor compound.   The hydrogen donor compound is 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -2-butan-1-one, 1-phenyl-2-mercapto-1,3-benzimidazole, N -Phenylglycine, 4,4'-bis (diethylamino) benzophenone, leucocrystal violet, 2-dimethylamino-2-methyl-1- (4-methoxyphenyl) propan-1-one-O-allyloxime, and tetra ( The photosensitive composition according to claim 5, which is at least one of (n-butyl) ammonium-n-butyltriphenylborate.   The photosensitive composition in any one of Claim 1 to 6 containing a heat-crosslinking agent and a thermosetting accelerator, and a binder contains alkali-soluble photocrosslinkable resin.   The photosensitive composition according to any one of claims 1 to 6, wherein the binder comprises a copolymer, and the copolymer has a structural unit derived from at least one of styrene and a styrene derivative.   The photosensitive composition in any one of Claim 1 to 7 in which a polymeric compound contains at least 1 sort (s) selected from the monomer which has a (meth) acryl group.   The photosensitive composition in any one of Claim 1 to 6 and 8 in which a polymeric compound contains the monomer which has at least any one of a urethane group and an aryl group.   The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The photosensitive composition as described.   A pattern forming material comprising at least a support and a photosensitive layer comprising the photosensitive composition according to any one of claims 1 to 11 on the support.   The pattern formation material of Claim 12 which has a cushion layer and a photosensitive layer in this order on a support body.   A photosensitive laminate comprising a photosensitive layer comprising the photosensitive composition according to claim 1 on a substrate.   The photosensitive laminated body of Claim 14 in which the photosensitive layer was formed with the pattern formation material in any one of Claims 12-13. Comprising the photosensitive laminate according to any one of claims 14 to 15,
A pattern forming apparatus comprising: a light irradiating unit capable of irradiating light; and a light modulating unit configured to modulate light from the light irradiating unit and to expose a photosensitive layer in the photosensitive laminate. .   The pattern formation method characterized by including at least exposing with respect to the photosensitive layer in the photosensitive laminated body in any one of Claim 14 to 15.   The pattern forming method according to claim 17, wherein the exposure is performed using a laser beam having a wavelength of 350 to 415 nm. The photosensitive layer has a light irradiating means, and n (where n is a natural number of 2 or more) two-dimensionally arranged pixel portions that receive and emit light from the light irradiating means, and have a pattern. An exposure head provided with a light modulation means capable of controlling the picture element portion according to information, wherein the column direction of the picture element portion forms a predetermined set inclination angle θ with respect to the scanning direction of the exposure head. Using the exposure head arranged in
With respect to the exposure head, the usable pixel part designating means designates the pixel part to be used for N double exposure (where N is a natural number of 2 or more) among the usable graphic elements.
For the exposure head, the pixel part control means controls the pixel part so that only the pixel part specified by the used pixel part specifying means is involved in exposure,
The pattern forming method according to claim 17, wherein the pattern forming method is performed by moving the exposure head relative to the photosensitive layer in a scanning direction.